CN114749036A - Hollow fiber heterogeneous membrane and preparation method and application thereof - Google Patents
Hollow fiber heterogeneous membrane and preparation method and application thereof Download PDFInfo
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- 239000012510 hollow fiber Substances 0.000 title claims abstract description 28
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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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
- B01D69/08—Hollow fibre membranes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
- A61M1/1621—Constructional aspects thereof
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- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/36—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits
- A61M1/3621—Extra-corporeal blood circuits
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- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/36—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits
- A61M1/3621—Extra-corporeal blood circuits
- A61M1/3666—Cardiac or cardiopulmonary bypass, e.g. heart-lung machines
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Abstract
The invention discloses a hollow fiber heterogeneous membrane and a preparation method and application thereof. The oxygen-containing membrane is prepared by a thermally induced phase separation method by taking poly-4-methyl-1-pentene as a membrane material and dioctyl phthalate as a diluent. The heterogeneous PMP oxide membrane with the hydrophilic surface and the hydrophobic main body is obtained by mixing amphiphilic block copolymer in membrane casting solution, extruding the uniformly mixed membrane casting solution through a spinning nozzle, performing phase separation and solidification on the membrane casting solution in a cooling water bath, simultaneously, automatically enriching a hydrophilic chain segment to the surface of the membrane, anchoring a polymer matrix in a hydrophobic segment, and performing in-situ surface modification on the membrane, extraction, drying and the like. The method has the advantages of simple operation, strong controllability, realization of one-step modification and the like. The modified membrane prepared by the invention is applied to extracorporeal membrane pulmonary oxygenation, the blood compatibility of the membrane is obviously improved, and the original high gas permeability of the PMP membrane is still maintained.
Description
Technical Field
The invention relates to the field of membranes, in particular to a poly-4-methyl-1-pentene (PMP) hollow fiber oxygen-containing membrane for realizing surface modification by utilizing a block copolymer, and a preparation method and application thereof.
Background
Extracorporeal membrane pulmonary oxygenation (ECMO) is an extracorporeal life support system that draws venous blood of low oxygen content and high carbon dioxide content from a patient through a blood pump, flows through an oxygenator, exchanges oxygen and carbon dioxide between the blood and a sweep gas, and then returns to the body, often for oxygenating blood, removing carbon dioxide, and is also known as an artificial lung. In recent years, the demand of ECMO rises year by year, and the ECMO is widely applied to treatment of acute respiratory failure, lung transplantation, cardiovascular diseases and the like, provides cardiopulmonary assistance support for patients in vitro, and wins precious time for the recovery of cardiopulmonary function. Membrane-type artificial lungs are one of the core components of ECMO and serve as a barrier between blood and gas to exchange carbon dioxide in blood and oxygen in air without direct contact through a permeable oxygen-containing membrane. The membrane type artificial lung takes a human alveolar membrane as a bionic prototype to simulate the gas exchange process at the alveolar part, the gas exchange capacity of the membrane needs to meet the physiological respiration requirement of a normal human body, and meanwhile, as a biomedical membrane directly contacted with the blood of the human body, the oxygenation membrane needs to have good blood compatibility and does not generate blood coagulation, hemolysis, immune reaction of an organism and the like when being contacted with the blood.
Poly-4-methyl-1-pentene (PMP) is a semi-crystalline polymer obtained by small molecule oriented polymerization, has high thermal stability and chemical stability, excellent gas permeability and lower surface tension, and becomes an ideal oxygenated membrane material of a new generation. PMP oxygenate membranes are prepared mainly by thermally induced phase separation methods, since PMP has a melting point as high as 240-. However, the directly prepared polymeric membrane often has no biocompatibility, and is difficult to meet clinical requirements, and particularly when the polymeric membrane is in contact with blood, reactions such as platelet adhesion, hemolysis, blood coagulation and the like are very easy to occur, and the realization of the performance of the oxygenation membrane is seriously influenced. Therefore, the blood compatibility of the membrane must be improved through surface modification, however, the PMP membrane has only methyl and methylene groups on the surface and has no active groups, so that great challenges are brought to the modification, and how to simply and efficiently realize the surface blood compatibility modification becomes a research hotspot.
The surface modification of the existing PMP membrane is realized by means of surface grafting, surface coating and the like, and the surface of the PMP membrane is required to be pretreated (for example, plasma activation) firstly[1]Depositing a mediating layer[2]Etc.), the number of modification steps is large and the gas permeability of the membrane itself is liable to be lowered. In order to give consideration to permeability and blood compatibility, the invention mixes the amphiphilic block copolymer in the membrane casting solution, in the membrane forming process, the hydrophilic chain segment of the amphiphilic block copolymer is automatically enriched to the surface of the membrane under the driving of chemical potential difference, and the hydrophobic segment anchors the polymer matrix to prevent the loss of the modifier, thereby realizing the in-situ surface modification of the PMP oxide membrane and constructing the PMP heterogeneous oxide membrane with the hydrophobic main body on the surface. The steric hindrance effect of the water molecule layer and the hydrophilic chain segment adsorbed on the surface of the hydrophilized membrane can effectively reduce the plasma eggThe adhesion of biological substances such as white blood and platelet, etc. so as to construct the inert membrane surface and improve the blood compatibility.
[ reference documents ]
[1]Huang X,Wang W P,Zheng Z,et al.Surface monofunctionalized polymethyl pentene hollow fiber membranes by plasma treatment and hemocompatibility modification for membrane oxygenators[J].Applied Surface Science,2016,362:355-363.
[2]PflaumM,Kuhn-Kauffeldt M,Schmeckebier S,et al.Endothelialization and characterization of titanium dioxide-coated gas-exchange membranes for application in the bioartificial lung[J].Acta Biomaterialia,2017,50:510-521.
Disclosure of Invention
Aiming at the prior art, the invention provides a hollow fiber heterogeneous oxygenizing membrane and a preparation method and application thereof. The preparation method is universal and controllable, the prepared oxygen-containing membrane has a heterogeneous structure with a hydrophobic main body with a hydrophilic surface, and the hydrophilic chain segment on the surface can effectively realize the improvement of the surface blood compatibility of the PMP membrane through a hydration layer effect and a steric hindrance effect. And because the block copolymer is enriched on the surface, the main structure and the performance of the membrane cannot be greatly influenced, so that the prepared oxygen-containing membrane still can keep excellent gas permeability.
In order to solve the technical problems, the hollow fiber heterogeneous membrane provided by the invention is composed of poly-4-methyl-1-pentene (PMP) and an amphiphilic block copolymer, the main body of the membrane is a loose porous structure formed by hydrophobic poly-4-methyl-1-pentene (PMP), and the amphiphilic block copolymer is enriched on the surface of the membrane; the amphiphilic block copolymer simultaneously has a hydrophilic chain segment and a hydrophobic chain segment, wherein the hydrophilic chain segment extends out of the membrane to construct a hydrophilic membrane surface, and the hydrophobic chain segment interacts with a poly-4-methyl-1-pentene (PMP) matrix to prevent loss of the modifier.
Further, the amphiphilic block copolymer has high thermal stability, and is melt-blended with poly-4-methyl-1-pentene (PMP) to form a homogeneous solution in the preparation process of the hollow fiber heterogeneous membrane.
Meanwhile, the invention also provides a preparation method of the hollow fiber heterogeneous membrane, and the preparation method can realize membrane formation and modification in one step and comprises the following steps:
step 1, blending poly-4-methyl-1-pentene (PMP) and a diluent dioctyl phthalate according to a mass ratio of 1:4-3:7, then adding 5-15% of amphiphilic block copolymer by mass percent, stirring and melting the mixed solution at 240 ℃ for 6 hours to form a homogeneous casting solution, standing for 12 hours and defoaming;
step 2, extruding and molding the casting solution defoamed in the step 1 through a spinning nozzle, then entering a cooling water bath at room temperature to carry out solid-liquid or liquid-liquid phase separation and curing and molding, and simultaneously finishing the surface enrichment of the amphiphilic block copolymer; then winding and collecting the filaments through a filament winding wheel to obtain a hollow fiber membrane;
step 3, soaking the membrane obtained in the step 2 in an extracting agent for 48 hours, and replacing the extracting agent every 12 hours to fully extract the diluent in the membrane;
and 4, drying the membrane obtained after the extraction in the step 3 in a vacuum oven at 40 ℃ for 12 hours to obtain the block copolymer modified poly-4-methyl-1-pentene hollow fiber heterogeneous membrane.
Further, the preparation method of the invention comprises the following steps:
in the step 1, the amphiphilic block copolymer is one of polyethylene-block-poly (ethylene glycol), Pluronic F127 and ethylene-vinyl alcohol copolymer (EVOH).
In the step 2, the process conditions of extrusion molding and winding and yarn winding are as follows: the extrusion speed of the feed liquid is 7.5-23ml/min, the flow rate of the core liquid is 20-50ml/min, and the rotating speed of the winding wheel is 0.64-1.15 m/s.
In the step 3, the extracting agent is absolute ethyl alcohol.
Compared with the prior art, the invention has the beneficial effects that:
the method can synchronously realize film formation and modification without subsequent reprocessing, has the advantages of simple preparation process, strong controllability, obvious surface modification effect, small influence on the performance of a film main body and wide application prospect in the aspect of blood compatibility modification. When the hollow fiber heterogeneous membrane prepared by the invention is used in the oxygenation process of extracorporeal membrane lung, the hydrophilicity of the membrane surface is shown as that the water contact angle is 66-83 degrees, the hemolysis rate of the membrane is 3.49-5.33 percent, and the gas permeation rate of the membrane is 1.79-2.55ml/(min cm & cm)2Bar). The modified membrane prepared by the invention has obviously improved blood compatibility and keeps higher gas permeability.
Drawings
Fig. 1 is a cross-sectional view of a heterogeneous PMP hollow fiber oxygenate membrane prepared in example 1.
FIG. 2 is a SEM image of the platelet adhesion of the membrane 1 obtained by the production method of the present invention;
FIG. 3 is a SEM image of platelet adhesion of an unmodified comparative membrane prepared according to the preparation method of comparative example 1;
Detailed Description
The hollow fiber heterogeneous membrane provided by the invention takes poly-4-methyl-1-pentene as a membrane material, consists of poly-4-methyl-1-pentene (PMP) and an amphiphilic block copolymer, and is prepared by a thermotropic phase separation method through a loose porous structure formed by hydrophobic poly-4-methyl-1-pentene (PMP). The specific design idea is that the amphiphilic block copolymer has high thermal stability, in the preparation process, the amphiphilic block copolymer and poly-4-methyl-1-pentene (PMP) are melted and blended to form a homogeneous solution, the uniformly mixed casting membrane solution is extruded by a spinning jet and then subjected to phase separation and solidification in a cooling water bath, the hydrophilic chain segment is driven by chemical potential to spontaneously enrich towards the surface of the membrane, the hydrophilic chain segment extends out of the membrane to construct the surface of the hydrophilic membrane, the hydrophobic chain segment anchors a polymer matrix, the hydrophobic chain segment interacts with a poly-4-methyl-1-pentene (PMP) matrix to prevent loss of a modifier, in-situ surface modification of the membrane is realized, and then the poly-4-methyl-1-pentene hollow fiber heterogeneous membrane modified by the block copolymer and provided with the hydrophilic surface and the hydrophobic main body is obtained through extraction, drying and the like. The method has the advantages of simple operation, strong controllability, realization of one-step modification and the like. The modified membrane prepared by the invention is applied to extracorporeal membrane pulmonary oxygenation, the main composition and structure of the membrane are basically unchanged, the original gas permeability can be well maintained, substances in blood are not directly contacted with the surface of the membrane by a water molecule layer adsorbed on the surface of the hydrophilic membrane, substances such as plasma protein and the like are difficult to approach the surface of the membrane due to large rejection volume generated by steric hindrance effect, and the two effects interact with each other, so that the blood compatibility of the surface of the membrane is effectively improved.
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
Example 1:
a heterogeneous PMP hollow fiber oxygenized membrane modified by block copolymer is prepared by the following steps:
step 1, respectively adding 200g of PMP raw material, 800g of dioctyl phthalate and 20g of polyethylene-block-poly (ethylene glycol) into a material liquid kettle, stirring the casting solution at 240 ℃ for 6h to form a homogeneous solution, and standing and defoaming for 12 h.
And 2, extruding the homogeneous casting film liquid obtained in the step 1 through a high-temperature spinning nozzle at the speed of 15ml/min for forming, wherein the flow rate of core liquid for forming a hollow structure is 40ml/min, solidifying and forming through cooling water, completing surface enrichment of the block copolymer, and completing winding and filament winding through a filament winding wheel, wherein the filament winding speed is 1.15 m/s.
And 3, soaking the membrane obtained in the step 2 in absolute ethyl alcohol for 48 hours to fully extract the membrane. The membrane was then dried in a vacuum oven at 40 ℃ for 12h, and the resulting heterogeneous PMP hollow fiber oxygenate membrane was designated as membrane 1, and fig. 1 is a cross-sectional electron micrograph of the membrane.
The water contact angle of the membrane 1 was 73 ° by static water contact angle test; by the platelet adhesion experiment and the hemolysis experiment, the SEM image of the platelet adhesion on the surface of the membrane 1 prepared in example 1 is shown in fig. 2, and the hemolysis rate is 3.63%; the oxygen permeation rate of the membrane 1 obtained by the single gas permeation experiment is 2.55ml/(min cm)2·bar)。
Example 2:
a block copolymer modified heterogeneous PMP hollow fiber oxygenated membrane was prepared, and the procedure of example 2 was substantially the same as that of example 1 except that in step 1, the amphiphilic block copolymer was changed from 20g of polyethylene-block-poly (ethylene glycol) to 15g of Pluronic F127, the PMP feedstock mass was changed from 200g to 300g, and the dioctyl phthalate mass was changed from 800g to 700 g. In the step 2, the extrusion speed of the feed liquid in the process conditions of extrusion molding and winding and yarn winding is changed from 15ml/min to 23ml/min, and the flow rate of the core liquid is changed from 40ml/min to 50 ml/min; the final film was designated film 2.
According to the same test method as in example 1: the water contact angle of membrane 2 was 83 °; the hemolysis rate is 5.33%; the oxygen permeation rate is 1.79ml/(min cm)2·bar)。
Example 3:
preparing a heterogeneous PMP hollow fiber oxygenized membrane modified by block copolymer,
the procedure of example 3 was substantially the same as in example 1 except that in step 1, the amphiphilic block copolymer was changed from 20g of polyethylene-block-poly (ethylene glycol) to 45g of ethylene-vinyl alcohol copolymer (EVOH). In the step 2, the extrusion speed of the feed liquid in the process conditions of extrusion molding and winding and yarn winding is changed from 15ml/min to 7.5ml/min, the flow rate of the core liquid is changed from 40ml/min to 20ml/min, the rotating speed of a winding wheel (namely the yarn winding speed) is changed from 1.15m/s to 0.64m/s, and the finally obtained film is marked as a film 3.
According to the same test method as in example 1: the water contact angle of membrane 3 was 66 °; the hemolysis rate is 3.49%; the oxygen permeation rate is 1.88ml/(min cm)2 bar)。
Comparative example 1:
the preparation method of the PMP hollow fiber oxygenized membrane without modification is different from the preparation method of the invention in the preparation step of comparative example 1, namely, amphiphilic block copolymer is not added in the preparation of membrane casting solution, and the specific steps are as follows:
adding 200g of PMP raw material into a material liquid kettle, stirring for 6 hours at 240 ℃ to form membrane casting liquid, standing and defoaming for 12 hours. Then, the mixture is extruded and molded through a high-temperature spinneret at the speed of 15ml/min, the flow rate of core liquid for forming a hollow structure is 40ml/min, the mixture is solidified and molded through cooling water, and winding are finished through a winding wheel, wherein the winding speed is 1.15 m/s. The obtained membrane is soaked in absolute ethyl alcohol for 48 hours, so that the membrane is fully extracted. The film was then dried in a vacuum oven at 40 ℃ for 12h, and the resulting film was designated as a comparative film.
The comparative film was tested for a water contact angle of 100 ° according to the same test method as in example 1; the SEM image of the platelet adhesion on the surface of the comparison membrane is shown in FIG. 3, and the hemolysis rate of the comparison membrane is tested to be 6.9%; the oxygen permeation rate of the test control membrane was 1.5ml/(min cm)2·bar)。
Water contact angle (. degree.), hemolysis rate (%) and oxygen permeation rate (ml/(min. cm) of the films obtained in examples 1 to 3 and comparative example 12Bar)) are shown in table 1.
TABLE 1 Properties of the films under different modification conditions
| Membrane 1 | Membrane 2 | Membrane 3 | Contrast film | |
| Water contact Angle (°) | 73 | 83 | 66 | 100 |
| Hemolysis ratio (%) | 3.63 | 5.33 | 3.49 | 6.9 |
| O2Permeation Rate (ml/(min cm)2·bar)) | 2.55 | 1.79 | 1.88 | 1.5 |
As can be seen from Table 1, the water contact angle of the modified membrane surface prepared by the preparation method of the invention is reduced to 66-83 degrees, and the hydrophilicity is obviously enhanced, which can be attributed to the successful enrichment of hydrophilic segments on the membrane surface at the cooling water bath, and the water contact angle is reduced along with the increase of the addition amount of the amphiphilic block copolymer. The hemolysis rate of the modified membrane is reduced to 3.49-5.33%, which shows that the damage to blood is reduced, and as can be seen from the attached drawings, the platelet adhesion amount on the surface of the membrane after surface modification is obviously reduced, which shows that the blood compatibility is effectively improved, which is mainly due to the following reasons: firstly, the decrease of the surface water contact angle, namely the improvement of the hydrophilicity, enables the surface of the PMP membrane to adsorb a layer of water-containing molecules, and the water-containing layers effectively reduce the exposed area of the real surface of the membrane in blood, thereby reducing the adhesion of blood platelets and the like; and secondly, the steric hindrance effect of the hydrophilic chain segment enriched on the surface of the membrane can also effectively prevent the attachment of substances in blood. Both effects work together to improve surface blood compatibility. And as can be seen from table 1, the amphiphilic block copolymer is only enriched on the surface in the membrane preparation process, and the main body composition and structure of the membrane are not significantly changed, so that the membrane modified by the block copolymer in situ still maintains the higher gas permeability of 1.79-2.55ml/(min · cm2 · bar).
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (7)
1. A hollow fiber heterogeneous membrane is characterized in that the membrane consists of poly-4-methyl-1-pentene (PMP) and an amphiphilic block copolymer, the main body of the membrane is a loose porous structure formed by hydrophobic poly-4-methyl-1-pentene (PMP), and the amphiphilic block copolymer is enriched on the surface of the membrane; the amphiphilic block copolymer simultaneously has a hydrophilic chain segment and a hydrophobic chain segment, wherein the hydrophilic chain segment extends out of the membrane to construct a hydrophilic membrane surface, and the hydrophobic chain segment interacts with a poly-4-methyl-1-pentene (PMP) matrix to prevent loss of a modifier.
2. The hollow fiber heterogeneous membrane according to claim 1, wherein the amphiphilic block copolymer has high thermal stability, and is melt blended with poly-4-methyl-1-pentene (PMP) to form a homogeneous solution during the preparation of the hollow fiber heterogeneous membrane.
3. A method for preparing the hollow fiber heterogeneous membrane according to claim 1 or 2, comprising the steps of:
step 1, blending poly-4-methyl-1-pentene (PMP) and a diluent dioctyl phthalate according to a mass ratio of 1:4-3:7, then adding 5-15% of amphiphilic block copolymer by mass percent, stirring and melting the mixed solution at 240 ℃ for 6 hours to form a homogeneous casting solution, standing for 12 hours and defoaming;
step 2, extruding and molding the casting solution defoamed in the step 1 through a spinning nozzle, then putting the casting solution into a cooling water bath at room temperature to perform solid-liquid or liquid-liquid phase separation and curing and molding, and simultaneously finishing the surface enrichment of the amphiphilic block copolymer; then winding and collecting the filaments through a filament winding wheel to obtain a hollow fiber membrane;
step 3, soaking the membrane obtained in the step 2 in an extracting agent for 48 hours, and replacing the extracting agent every 12 hours to fully extract the diluent in the membrane;
and 4, drying the membrane obtained after the extraction in the step 3 in a vacuum oven at 40 ℃ for 12 hours to obtain the block copolymer modified poly-4-methyl-1-pentene hollow fiber heterogeneous membrane.
4. The method of claim 3, wherein in step 1, the amphiphilic block copolymer is one of polyethylene-block-poly (ethylene glycol), Pluronic F127 and ethylene vinyl alcohol (EVOH).
5. The preparation method according to claim 3, wherein in the step 2, the process conditions of extrusion molding and winding for filament winding are as follows: the extrusion speed of the feed liquid is 7.5-23ml/min, the flow rate of the core liquid is 20-50ml/min, and the rotating speed of the winding wheel is 0.64-1.15 m/s.
6. The method according to claim 3, wherein in step 3, the extractant is absolute ethanol.
7. Use of a hollow fiber heterogeneous membrane in an extracorporeal membrane lung oxygenator (ECMO), wherein the hollow fiber heterogeneous membrane prepared by the preparation method according to any one of claims 3 to 6 is used in the extracorporeal membrane lung oxygenating process, the membrane surface hydrophilicity is shown as a water contact angle of 66-83 degrees, the membrane hemolysis rate is 3.49-5.33%, and the membrane gas permeation rate is 1.79-2.55 ml/(min-cm)2·bar)。
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| CN113398773A (en) * | 2021-06-11 | 2021-09-17 | 清华大学 | Poly (4-methyl-1-pentene) hollow fiber alloy membrane and preparation method and application thereof |
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