CN115400600A - Hollow fiber composite membrane and preparation method and application thereof - Google Patents
Hollow fiber composite membrane and preparation method and application thereof Download PDFInfo
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- CN115400600A CN115400600A CN202211021897.7A CN202211021897A CN115400600A CN 115400600 A CN115400600 A CN 115400600A CN 202211021897 A CN202211021897 A CN 202211021897A CN 115400600 A CN115400600 A CN 115400600A
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- hollow fiber
- fiber composite
- polyether sulfone
- spinning solution
- composite membrane
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D69/087—Details relating to the spinning process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides a hollow fiber composite membrane and a preparation method and application thereof, wherein the preparation method of the hollow fiber composite membrane comprises the following steps: uniformly mixing the modified polyether sulfone mixture, the hydrophilic additive and the organic solvent to prepare a separation layer spinning solution; uniformly mixing the modified polyether sulfone mixture, a plasticizer, a pore-forming agent and an organic solvent to prepare a supporting layer spinning solution; forming an initial membrane by a coextrusion process of the separation layer spinning solution, the support layer spinning solution and the core solution, and solidifying and cleaning the initial membrane to obtain the hollow fiber composite membrane; the modified polyethersulfone mixture comprises polyethersulfone and/or end-hydroxylated polyethersulfone. The invention solves the problems that the existing hollow fiber membrane is not easy to realize large-scale production, and the performance consistency is poor, thereby increasing the production cost of the hollow fiber membrane.
Description
Technical Field
The invention relates to the technical field of blood purification materials, in particular to a hollow fiber composite membrane and a preparation method and application thereof.
Background
Hemodialysis, which is a blood purification technique for removing harmful substances and excessive water from blood by using the principles of dispersion, ultrafiltration and convection, is one of the most common renal replacement therapy methods, and can also be used for treating drug overdose or toxicosis. Hemofiltration is a medical technique that removes excess water and uremic toxins in the body in a convective manner. Hemodiafiltration is a combination of hemodialysis and hemofiltration, and has the advantages of two modes of treatment, and can remove solutes by two mechanisms, namely diffusion and convection.
Ultrafiltration membranes are the most important component for the realization of the above-mentioned medical technology. The surface chemical composition and the hydrophilic property of the ultrafiltration membrane have great influence on the blood compatibility of the membrane. At present, the commonly used hemodialysis, hemofiltration and hemodiafiltration membranes comprise Polysulfone (PSF) and polyether sulfone (PES), and the two membrane materials have poor hydrophilicity, so the blood compatibility is not satisfactory. The common improvement method is to add hydrophilic substances such as polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) and the like to carry out blending modification or carry out coating modification on the surface of the membrane to prepare modified hemodialysis, hemofiltration and hemodiafiltration membranes, improve the hydrophilicity of membrane materials and improve the blood compatibility of the membrane materials.
However, the membrane is prepared by blending modification by adding hydrophilic substances such as polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG), and the like, and although the large-scale production is convenient and easy to realize, the separation layer and the support layer of the membrane belong to the same formula system, and the formulas of the separation layer and the support layer are difficult to be respectively regulated and controlled according to actual needs in the aspect of membrane structure control, that is, the differential control of the separation layer and the support layer on the structure and performance cannot be realized through formula regulation and control. The method can be used for preparing the base film and the coating layer in a distributed manner according to actual needs, but large-scale production is not easy to realize, the performance consistency is poor, and the production cost of the film is increased.
In view of the above, there is a need for a method for preparing a hollow fiber composite membrane, which is easy to realize mass production, has good consistency of performance, and can reduce production cost.
Disclosure of Invention
The invention aims to solve the problems that the existing hollow fiber membrane is not easy to realize large-scale production, and the performance consistency is poor, so that the production cost of the hollow fiber membrane is increased.
In order to solve the above problems, a first aspect of the present invention provides a method for preparing a hollow fiber composite membrane, comprising the steps of:
uniformly mixing the modified polyether sulfone mixture, the hydrophilic additive and the organic solvent to prepare a separation layer spinning solution;
uniformly mixing the modified polyether sulfone mixture, a plasticizer, a pore-foaming agent and an organic solvent to prepare a supporting layer spinning solution;
forming an initial membrane by the aid of a coextrusion process through the separation layer spinning solution, the supporting layer spinning solution and the core solution, and solidifying and cleaning the initial membrane to obtain a hollow fiber composite membrane;
wherein the modified polyethersulfone mixture comprises polyethersulfone and/or end-hydroxylated polyethersulfone.
Further, the separation layer spinning solution is prepared by adopting the following method:
mixing 15 to 35 mass percent of modified polyether sulfone mixture, 25 to 40 mass percent of hydrophilic additive and 45 to 60 mass percent of organic solvent at the temperature of between 30 and 80 ℃ for 12 to 24 hours, and filtering and defoaming in vacuum to prepare a separation layer spinning solution.
Further, the hydrophilic additive is one or two of polyethylene glycol, cellulose acetate, polyvinyl alcohol and polymethyl methacrylate;
the organic solvent is one or the combination of two of triethyl phosphate, N-methylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Further, the supporting layer spinning solution is prepared by adopting the following method:
mixing 10 to 25 mass percent of modified polyether sulfone mixture, 5 to 30 mass percent of plasticizer, 15 to 40 mass percent of pore-forming agent and 30 to 65 mass percent of organic solvent at 30 to 80 ℃ for 12 to 24 hours, and filtering and defoaming in vacuum to prepare the supporting layer spinning solution.
Further, the plasticizer is one or the combination of two of polyvinylpyrrolidone, polyethylene glycol, carboxymethyl cellulose, hydroxyethyl cellulose and polymethyl methacrylate;
the pore-foaming agent is one or the combination of two of ethanol, ethylene glycol, isopropanol, ethylene glycol monomethyl ether, diethylene glycol and glycerol;
the organic solvent is one or the combination of two of triethyl phosphate, N-methylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Further, the modified polyether sulfone mixture in the separation layer spinning solution comprises polyether sulfone and end-hydroxylated polyether sulfone, or the modified polyether sulfone mixture is end-hydroxylated polyether sulfone;
the modified polyether sulfone mixture in the supporting layer spinning solution comprises polyether sulfone and end-hydroxylated polyether sulfone, or the modified polyether sulfone mixture is polyether sulfone.
Further, the initial film is prepared by the following method:
and simultaneously extruding the separation layer spinning solution, the support layer spinning solution and the core liquid from a three-hole annular spinneret to prepare an initial membrane, wherein the three-hole annular spinneret comprises a core liquid channel, a separation layer solution channel and a support layer solution channel which are sequentially arranged from inside to outside, the core liquid is extruded from the core liquid channel, the separation layer spinning solution is extruded from the separation layer solution channel, and the support layer spinning solution is extruded from the support layer solution channel.
Further, the initial film is solidified using the following method:
the initial film is sequentially solidified through an air section and a solidification bath, wherein the relative humidity of the air section is 30-90%, the temperature is 30-50 ℃, and the residence time of the initial film in the air section is 0.5-1.5 s; the coagulating bath is prepared by mixing water and a pore-forming agent, or the coagulating bath is prepared by mixing water and an organic solvent, and the liquid level height of the coagulating bath is kept constant.
In a second aspect, the present invention provides a hollow fiber composite membrane, which is prepared by the method for preparing the hollow fiber composite membrane according to any one of the first aspect.
In a third aspect of the present invention, there is provided a use of the hollow fiber composite membrane according to the second aspect in hemodialysis.
According to the preparation method of the hollow fiber composite membrane, the separation layer spinning solution and the support layer spinning solution are prepared from the modified polyether sulfone mixture, the modified polyether sulfone mixture comprises polyether sulfone and/or end-hydroxylated polyether sulfone, and the end-hydroxylated polyether sulfone is non-water-soluble hydrophilic modified polyether sulfone which is blended with the polyether sulfone to form a membrane, so that the hydrophilic performance of the hollow fiber composite membrane can be improved, and the blood compatibility of the hollow fiber composite membrane can be improved; in the process of film formation, the terminal hydroxyl in the terminal hydroxyl polyether sulfone can form hydrogen bonds with hydrophilic substances (such as water-soluble PVP or PEG molecules) so that the hydrophilic substances are anchored on the surface of the hollow fiber composite film, the blood compatibility of the hollow fiber composite film can be further improved, and the terminal hydroxyl in the terminal hydroxyl polyether sulfone is connected with the hydrophilic substances through the hydrogen bonds so that the hydrophilic substances can be more firmly combined on the film-forming substances, and the phenomena of falling off or dissolution of the hydrophilic substances and the like are avoided; the polyether sulfone has excellent mechanical properties, and the structural strength of the hollow fiber composite membrane can be improved by taking the polyether sulfone as a supporting layer spinning solution; in addition, through separately regulating and controlling the membrane preparation formulas of the separation layer spinning solution and the supporting layer spinning solution, a hydrophilic separation layer can be prepared, the surface and the pores of the separation layer form hydration layers to improve the hydrophilicity so as to improve the blood compatibility of the hollow fiber composite membrane, meanwhile, the wall thickness of the separation layer can be regulated and controlled, and the filtration resistance of the hollow fiber composite membrane is reduced.
In addition, the separation layer spinning solution, the supporting layer spinning solution and the core solution are prepared into the hollow fiber composite membrane through a co-extrusion process by a co-extrusion process, one-step membrane forming can be realized, large-scale production is facilitated, and membrane forming is performed through the co-extrusion process, so that the hydrophilic separation layer which is in direct contact with blood can be combined on the supporting layer, the blood compatibility of the hollow fiber composite membrane is improved, membrane forming formulas of the separation layer and the supporting layer can be separately regulated and controlled, the structure of the hollow fiber composite membrane is optimized, and the performance of the hollow fiber composite membrane is improved.
Drawings
FIG. 1 is a flow chart of a method for preparing a hollow fiber composite membrane according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a three-hole annular spinneret provided in accordance with an embodiment of the present invention;
FIG. 3 is a sectional electron microscope image of a hollow fiber composite membrane prepared in example 1 of the present invention;
FIG. 4 is a sectional electron microscope image of a separation layer of a hollow fiber membrane obtained in example 1 of the present invention.
Description of reference numerals:
200-bore fluid channel; 210-separating layer solution channels; 220-support layer solution channels.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
In addition, the terms "comprising," "including," "containing," and "having" are intended to be non-limiting, i.e., that other steps and other ingredients can be added which do not affect the result. Materials, equipment and reagents were all commercially available unless otherwise specified.
In addition, although the steps in the preparation are described in the form of step S100, step S200, step S300, etc., this description is only for ease of understanding, and the form of step S100, step S200, step S300, etc. does not represent a limitation on the order of the steps.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a hollow fiber composite membrane, including the following steps:
step S100, uniformly mixing the modified polyether sulfone mixture, the hydrophilic additive and the organic solvent to prepare a separation layer spinning solution;
step S200, uniformly mixing the modified polyether sulfone mixture, the plasticizer, the pore-forming agent and the organic solvent to prepare a supporting layer spinning solution;
s300, forming an initial membrane by a coextrusion process through the separation layer spinning solution, the supporting layer spinning solution and the core solution, and solidifying and cleaning the initial membrane to obtain the hollow fiber composite membrane;
wherein the modified polyether sulfone mixture comprises polyether sulfone and/or end hydroxylated polyether sulfone.
According to the preparation method of the hollow fiber composite membrane, the separation layer spinning solution and the support layer spinning solution are prepared from the modified polyether sulfone mixture, the modified polyether sulfone mixture comprises polyether sulfone and/or end hydroxyl polyether sulfone, the end hydroxyl polyether sulfone is water-insoluble hydrophilic modified polyether sulfone, and the water-insoluble hydrophilic modified polyether sulfone is blended with the polyether sulfone to form a membrane, so that the hydrophilic performance of the hollow fiber composite membrane can be improved, and the blood compatibility of the hollow fiber composite membrane can be improved; in the process of film formation, the terminal hydroxyl in the terminal hydroxyl polyether sulfone can form hydrogen bonds with hydrophilic substances (such as water-soluble PVP or PEG molecules) so that the hydrophilic substances are anchored on the surface of the hollow fiber composite film, the blood compatibility of the hollow fiber composite film can be further improved, and the terminal hydroxyl in the terminal hydroxyl polyether sulfone is connected with the hydrophilic substances through the hydrogen bonds so that the hydrophilic substances can be more firmly combined on the film-forming substances, and the phenomena of falling off or dissolution of the hydrophilic substances and the like are avoided; the polyether sulfone has excellent mechanical properties, and the structural strength of the hollow fiber composite membrane can be improved by taking the polyether sulfone as a supporting layer spinning solution; in addition, in this embodiment, by separately adjusting and controlling the membrane preparation formulas of the separation layer spinning solution and the support layer spinning solution, a hydrophilic separation layer can be prepared, so that a hydration layer is formed on the surface and the pores of the separation layer to improve hydrophilicity, so as to improve blood compatibility of the hollow fiber composite membrane, and meanwhile, the wall thickness of the separation layer can be adjusted and controlled, so as to reduce filtration resistance of the hollow fiber composite membrane, while the support layer can prepare a porous layer by adjusting the membrane preparation formula of the support layer spinning solution, so as to further reduce filtration resistance of the hollow fiber composite membrane, and the separation layer spinning solution and the support layer spinning solution use main body materials with similar structures, so that interface molecules of the separation layer and the support layer can be wound more firmly in a further membrane forming process, so that the bonding strength of the separation layer and the support layer is more stable.
In addition, the separation layer spinning solution, the supporting layer spinning solution and the core solution are prepared into the hollow fiber composite membrane through a co-extrusion process by a co-extrusion process, one-step membrane forming can be realized, large-scale production is facilitated, and membrane forming is performed through the co-extrusion process, so that the hydrophilic separation layer which is in direct contact with blood can be combined on the supporting layer, the blood compatibility of the hollow fiber composite membrane is improved, membrane forming formulas of the separation layer and the supporting layer can be separately regulated and controlled, the structure of the hollow fiber composite membrane is optimized, and the performance of the hollow fiber composite membrane is improved.
Specifically, the separation layer spinning solution may be prepared in step S100 by the following method:
stirring 15 to 35 mass percent of modified polyether sulfone mixture, 25 to 40 mass percent of hydrophilic additive and 45 to 60 mass percent of organic solvent at the temperature of between 30 and 80 ℃ for 12 to 24 hours until the mixture is uniformly mixed, and filtering and defoaming in vacuum for 10 to 12 hours to prepare a clear and transparent separation layer spinning solution.
The dosage proportion of each component in the spinning solution of the separation layer is limited within a certain range, which is favorable for improving the quality of the hollow fiber composite membrane and further improving the blood compatibility of the hollow fiber composite membrane, and is also favorable for regulating and controlling the wall thickness of the separation layer so as to further reduce the filtration resistance of the hollow fiber composite membrane and improve the efficiency of blood purification.
The modified polyether sulfone mixture comprises polyether sulfone and end-hydroxylated polyether sulfone, or the modified polyether sulfone mixture is end-hydroxylated polyether sulfone.
If the modified polyethersulfone mixture comprises polyethersulfone and end-hydroxylated polyethersulfone, then the polyethersulfone and end-hydroxylated polyethersulfone may be combined in any ratio and are not further defined in this example. For example: the polyethersulfone and the terminally hydroxylated polyethersulfone may be mixed in 25% polyethersulfone and 75% terminally hydroxylated polyethersulfone.
The end-hydroxylated polyethersulfone in the present example was purchased from the market and had the following molecular structure:
in this embodiment, the hydrophilic additive is one or a combination of two of polyethylene glycol, cellulose acetate, polyvinyl alcohol and polymethyl methacrylate, wherein the polyethylene glycol may be one or a combination of two of PEG200, PEG400, PEG600, PEG800 and PEG 1000. The organic solvent is one or the combination of two of triethyl phosphate, N-methylformamide, N-dimethylacetamide and N-methylpyrrolidone. Compared with other hydrophilic additives and organic solvents in the prior art, when the hydrophilic additives and the organic solvents are adopted, the hydrophilicity and the biocompatibility of the obtained hollow fiber composite membrane can be further improved.
When the spinning solution is prepared, the polyether sulfone, the end-hydroxylated polyether sulfone and the hydrophilic additive are dissolved in the organic solvent together, so that blending is realized, and the hollow fiber composite membrane with good blood compatibility is prepared and hydrophilic substances are firmly combined to the modified polyether sulfone mixture by virtue of the advantages of the combination of blending and hydrogen bonds.
Specifically, the supporting layer spinning solution may be prepared in step S200 by the following method:
stirring 10 to 25 mass percent of modified polyether sulfone mixture, 5 to 30 mass percent of plasticizer, 15 to 40 mass percent of pore-forming agent and 30 to 65 mass percent of organic solvent at 30 to 80 ℃ for 12 to 24 hours until the mixture is uniformly mixed, and filtering and defoaming in vacuum for 10 to 12 hours to prepare clear and transparent supporting layer spinning solution.
The proportion of the dosage of each component in the spinning solution of the supporting layer is limited in a certain range, the pore diameter of the supporting layer is favorably regulated, and the supporting layer with a porous structure is prepared, so that the filtering resistance of the hollow fiber composite membrane is further reduced, and the efficiency of blood purification is favorably improved.
The modified polyether sulfone mixture comprises polyether sulfone and end-hydroxylated polyether sulfone, or the modified polyether sulfone mixture is polyether sulfone.
It should be noted that if the separation layer spinning solution contains polyethersulfone and end-hydroxylated polyethersulfone, the supporting layer spinning solution may contain both polyethersulfone and end-hydroxylated polyethersulfone, or only polyethersulfone; if the separation layer spinning solution contains the end-hydroxylated polyether sulfone, the supporting layer spinning solution can contain both polyether sulfone and the end-hydroxylated polyether sulfone, or only contain polyether sulfone, so long as the modified polyether sulfone mixture in the separation layer spinning solution and the modified polyether sulfone mixture in the supporting layer spinning solution can contain both polyether sulfone and the end-hydroxylated polyether sulfone, and blending and membrane preparation of the polyether sulfone and the end-hydroxylated polyether sulfone are ensured, so that the hydrophilic performance of the hollow fiber composite membrane is improved, and the blood compatibility of the hollow fiber composite membrane is improved.
If the modified polyethersulfone mixture comprises polyethersulfone and end-hydroxylated polyethersulfone, then the polyethersulfone and end-hydroxylated polyethersulfone may be combined in any ratio and are not further defined in this example. For example: the polyethersulfone and the terminally hydroxylated polyethersulfone may be mixed in the range of 50% polyethersulfone to 50% terminally hydroxylated polyethersulfone.
In this embodiment, the plasticizer is one or a combination of two of polyvinylpyrrolidone, polyethylene glycol, carboxymethyl cellulose, hydroxyethyl cellulose and polymethyl methacrylate, where the polyvinylpyrrolidone may be one or a combination of two of PVPK15, PVPK17, PVPK30 and PVPK60, and the polyethylene glycol may be one or a combination of two of PEG8000, PEG10000 and PEG 20000. The pore-forming agent is one or the combination of two of ethanol, ethylene glycol, isopropanol, ethylene glycol monomethyl ether, diethylene glycol and glycerol. The organic solvent is one or the combination of two of triethyl phosphate, N-methylformamide, N-dimethylacetamide and N-methylpyrrolidone. Compared with other types of plasticizers, pore-forming agents and organic solvents in the prior art, when the plasticizers, pore-forming agents and organic solvents are adopted, the filtration resistance of the obtained hollow fiber composite membrane can be further improved, and the bonding strength of the separation layer and the support layer can be further improved.
Specifically, the initial film may be prepared in step S300 by the following method:
and extruding the separation layer spinning solution, the support layer spinning solution and the core liquid from the three-hole annular spinneret at the same time to prepare the initial membrane, wherein the three-hole annular spinneret comprises a core liquid channel, a separation layer solution channel and a support layer solution channel which are sequentially arranged from inside to outside, the core liquid is extruded from the core liquid channel, the separation layer spinning solution is extruded from the separation layer solution channel, and the support layer spinning solution is extruded from the support layer solution channel.
The structure of the three-hole annular spinneret is shown in fig. 2, the three-hole annular spinneret comprises a core liquid channel 200, a separation layer solution channel 210 and a support layer solution channel 220 which are sequentially arranged from inside to outside, the core liquid channel 200 is a circular channel, the separation layer solution channel 210 and the support layer solution channel 220 are annular channels, and the core liquid, the separation layer spinning solution and the support layer spinning solution are sequentially arranged from inside to outside to form an initial membrane with good blood compatibility and mechanical performance.
After the initial membrane is prepared, the initial membrane firstly passes through an air section, the relative humidity of the air section is 30-90%, the temperature is 30-50 ℃, and the retention time of the initial membrane in the air section is 0.5-1.5 s; after passing through the air section, the initial membrane enters a coagulating bath for coagulation, the liquid level of the coagulating bath is kept constant, and the initial membrane is fully coagulated and formed in the coagulating bath to prepare the hollow fiber composite membrane.
Through passing through the coagulating bath with initial membrane process air section earlier again in this embodiment, be favorable to making the aperture of hollow fiber composite membrane inner wall to the aperture crescent of hollow fiber composite membrane outer wall to reduce the thickness of hollow fiber composite membrane inner wall, thereby reduce the resistance of hollow fiber composite membrane dialysis in-process, be favorable to improving blood purification's efficiency.
In this embodiment, the bore fluid may be prepared by mixing a pore-forming agent and an organic solvent, or by mixing water and an organic solvent.
In order to further improve the hydrophilicity and biocompatibility of the obtained hollow fiber composite membrane, the pore-foaming agent comprises one or the combination of two of ethanol, ethylene glycol, isopropanol, ethylene glycol monomethyl ether, diethylene glycol and glycerol; the organic solvent comprises one or the combination of two of triethyl phosphate, N-methylformamide, N-dimethylacetamide and N-methylpyrrolidone.
In this example, the coagulation bath is prepared by mixing water and an organic solvent, and specifically, the coagulation bath is prepared by uniformly mixing 40 to 90 mass% of water and 10 to 60 mass% of an organic solvent.
Or, in this embodiment, the coagulation bath is prepared by mixing water and a pore-forming agent, specifically, by uniformly mixing 30 to 80 mass% of water and 20 to 70 mass% of a pore-forming agent, the coagulation bath is prepared.
In order to further improve the hydrophilicity and biocompatibility of the resulting hollow fiber composite membrane, the organic solvent includes one or a combination of two of triethyl phosphate, N-methylformamide, N-dimethylacetamide and N-methylpyrrolidone.
And after full solidification in a coagulating bath and before the hollow fiber composite membrane is prepared, washing the shaped initial membrane with water, and drying after the washing is finished to obtain the hollow fiber composite membrane, wherein the water temperature is 80-100 ℃ during the washing, and the drying temperature is 30-60 ℃.
Chemical substances such as additives and solvents in the hollow fiber composite membrane can be removed through washing, residual quantity of the chemical substances has great influence on blood compatibility, moisture in the hollow fiber composite membrane is removed through drying, internal stress can be eliminated, and size stability of the hollow fiber composite membrane is improved.
In this example, the water used is purified water or water for hemodialysis.
In order to further illustrate the present invention, the following examples are given to further illustrate the present invention. The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified; the materials, reagents and the like used in the examples of the present invention were commercially available, unless otherwise specified, wherein the terminally hydroxylated polyethersulfone was purchased from SUMITOMO CHEMICAL and was available as hydroxyterminedpes.
Example 1
The embodiment provides a preparation method of a hollow fiber composite membrane, which comprises the following steps:
(1) Uniformly stirring and mixing 70wt% of polyether sulfone and 30wt% of hydroxyl-terminated polyether sulfone to obtain a modified polyether sulfone mixture; stirring 18wt% of modified polyether sulfone mixture, 40wt% of hydrophilic additive PEG600 and 52wt% of organic solvent N, N-dimethylacetamide at 50 ℃ for 24 hours until the mixture is uniformly mixed, and filtering and vacuum defoaming for 12 hours to prepare a clear and transparent separation layer spinning solution;
stirring 16 mass percent of polyether sulfone, 8 mass percent of plasticizer polyvinylpyrrolidone, 25 mass percent of pore-forming agent ethylene glycol monomethyl ether and 51 mass percent of organic solvent N, N-dimethylacetamide at 50 ℃ for 24 hours until the components are uniformly mixed, and filtering and vacuum defoaming for 12 hours to prepare a clear and transparent supporting layer spinning solution;
stirring and mixing 5wt% of organic solvent N, N-dimethylacetamide and 95wt% of water uniformly to prepare core liquid;
70wt% of water and 30wt% of organic solvent N, N-dimethylacetamide are stirred and mixed evenly to prepare the coagulating bath.
(2) And extruding the separation layer spinning solution, the support layer spinning solution and the core liquid from a three-hole annular spinneret at the same time, wherein the three-hole annular spinneret comprises a core liquid channel, a separation layer solution channel and a support layer solution channel which are sequentially arranged from inside to outside, the core liquid is extruded from the core liquid channel, the separation layer spinning solution is extruded from the separation layer solution channel, and the support layer spinning solution is extruded from the support layer solution channel to prepare the initial membrane.
(3) The method comprises the following steps of enabling an initial membrane to pass through an air section, keeping the temperature and the humidity of the air section constant, keeping the relative humidity of the air section at 60% and the temperature at 40 ℃, keeping the retention time of the initial membrane in the air section at 1s, enabling the initial membrane subjected to phase pre-separation to enter a coagulation bath for coagulation, keeping the liquid level of the coagulation bath constant, enabling the initial membrane subjected to phase pre-separation to enter a cleaning water tank after the initial membrane subjected to phase pre-separation is fully coagulated in the coagulation bath, keeping the temperature of the cleaning water tank at 90 ℃, enabling the initial membrane subjected to cleaning to enter a circulating hot air drying box after the cleaning is finished, and drying at 45 ℃ to obtain the hollow fiber composite membrane.
The cross-sectional electron microscope image of the hollow fiber composite membrane prepared in this example is shown in fig. 3, and the cross-sectional electron microscope image of the separation layer of the hollow fiber composite membrane prepared in this example is shown in fig. 4. As can be seen from fig. 3 to 4, the interface between the separation layer and the support layer of the hollow fiber composite membrane manufactured in this embodiment is firmly bonded, which is beneficial to improving the mechanical strength of the hollow fiber composite membrane, and the support layer is of a porous structure, and the wall thickness of the separation layer is small, which is beneficial to reducing the filtration resistance of the hollow fiber composite membrane and improving the efficiency of blood purification.
Example 2
The present embodiment provides a method for preparing a hollow fiber composite membrane, the method for preparing a hollow fiber composite membrane in this embodiment is substantially the same as the method for preparing the hollow fiber composite membrane in embodiment 1, except that the ratios of the components in the separation layer spinning solution and the support layer spinning solution are different, specifically:
uniformly stirring and mixing 20wt% of polyether sulfone and 80wt% of hydroxyl-terminated polyether sulfone to obtain a modified polyether sulfone mixture; stirring 18wt% of modified polyether sulfone mixture, 35wt% of hydrophilic additive PEG600 and 57wt% of organic solvent N, N-dimethylacetamide at 50 ℃ for 24 hours until the mixture is uniformly mixed, and filtering and vacuum defoaming for 12 hours to prepare a clear and transparent separation layer spinning solution;
the preparation method comprises the following steps of stirring 16 mass percent of polyether sulfone, 8 mass percent of plasticizer polyvinylpyrrolidone, 28 mass percent of pore-forming agent glycerol and 48 mass percent of organic solvent N, N-dimethylacetamide at 50 ℃ for 24 hours until the materials are uniformly mixed, and filtering and defoaming in vacuum for 12 hours to prepare a clear and transparent supporting layer spinning solution.
Example 3
The present embodiment provides a method for preparing a hollow fiber composite membrane, the method for preparing a hollow fiber composite membrane in this embodiment is substantially the same as the method for preparing the hollow fiber composite membrane in embodiment 1, except that the ratios of the components in the separation layer spinning solution and the support layer spinning solution are different, specifically:
the modified polyether sulfone mixture is only hydroxyl-terminated polyether sulfone; stirring 18wt% of modified polyether sulfone mixture, 35wt% of hydrophilic additive PEG600 and 57wt% of organic solvent N, N-dimethylacetamide at 50 ℃ for 24 hours until the mixture is uniformly mixed, and filtering and vacuum defoaming for 12 hours to prepare a clear and transparent separation layer spinning solution;
the preparation method comprises the following steps of stirring 15 mass percent of polyether sulfone, 10 mass percent of plasticizer polyvinylpyrrolidone, 27 mass percent of pore-forming agent glycerol and 48 mass percent of organic solvent N, N-dimethylacetamide at 50 ℃ for 24 hours until the materials are uniformly mixed, and filtering and defoaming in vacuum for 12 hours to prepare a clear and transparent supporting layer spinning solution.
Example 4
The present embodiment provides a method for preparing a hollow fiber composite membrane, which is substantially the same as the method for preparing the hollow fiber composite membrane in embodiment 1, except that the ratios of components in a separation layer spinning solution and a support layer spinning solution are different, specifically:
uniformly stirring and mixing 20wt% of polyether sulfone and 80wt% of hydroxyl-terminated polyether sulfone to obtain a modified polyether sulfone mixture; stirring 18wt% of modified polyether sulfone mixture, 35wt% of hydrophilic additive PEG400 and 57wt% of organic solvent N, N-dimethylacetamide at 50 ℃ for 24 hours until the mixture is uniformly mixed, and filtering and vacuum defoaming for 12 hours to prepare a clear and transparent separation layer spinning solution;
stirring 8 mass percent of polyether sulfone, 8 mass percent of hydroxyl-terminated polyether sulfone, 9 mass percent of plasticizer polyvinylpyrrolidone, 25 mass percent of pore-forming agent ethylene glycol monomethyl ether and 50 mass percent of organic solvent N, N-dimethylacetamide at 50 ℃ for 24 hours until the components are uniformly mixed, and filtering and defoaming in vacuum for 12 hours to prepare a clear and transparent supporting layer spinning solution.
Testing the performance of the hollow fiber composite membrane of the embodiment 1 to the embodiment 4, and mainly adopting an inner surface contact angle, a calcium restoring time and a hemolysis rate to characterize the blood compatibility of the hollow fiber composite membrane, wherein the smaller the inner surface contact angle is, the better the hydrophilicity of the surface of the hollow fiber composite membrane is; the longer the recalcification time, the lower the hemolysis rate, indicating better blood compatibility. The specific test method is as follows:
1. internal surface contact Angle test
And (3) flatly paving and pasting the hollow fiber composite membrane sample on a carrying platform, leveling a base line, dripping about 5 mu L of deionized water on the membrane surface, adjusting a rotary tester, and reading a contact angle. Three parallel samples are measured on each hollow fiber composite membrane, 7 test points are taken on each sample, and the average value of the test results is taken.
2. Recalcification Time (PRT) test
(1) Taking 5mL of bovine whole blood, centrifuging (2000 g, about 4411r/min,10 min), and taking supernatant to obtain Platelet Poor Plasma (PPP);
(2) Placing the hollow fiber composite membrane into a 24-hole cell culture plate, labeling, dripping 0.1mL of PPP onto the surface of the membrane in a constant-temperature water bath at 37 ℃, and keeping for one minute;
(3) 0.1mL of 0.025mol/L CaCl 2 solution preheated to 37 ℃ was added dropwise to the membrane surface, the timing was stopped when the appearance of the first fibrin thread was observed, and the recalcification time was recorded.
3. Hemolytic Rate (HR) test
(1) Washing the hollow fiber composite membrane with deionized water for 10min, and then washing the membrane with 0.9% NaCl solution by mass fraction for 10min;
(2) Soaking the membrane in 0.9% NaCl solution at 37 deg.C for 30min;
(3) Adding 200 mu L of bovine whole blood into a membrane-containing NaCl solution, a membrane-free NaCl solution and pure water respectively, and keeping the temperature constant at 37 ℃ for 1h;
(4) The above samples were centrifuged (800 g, about 2790r/min,10 min) and the supernatant taken and the absorbance measured at 545nm using an ultraviolet spectrophotometer. 0.9wt% NaCl aqueous solution was used as a negative control, deionized water was used as a positive control, and the hemolysis rate was calculated from the following equation (1):
HR = (AS-AN)/(AP-AN). Times.100% equation (1)
In the formula: AS-absorbance of the sample; AN-absorbance of negative control; AP-absorbance of positive control.
The hollow fiber composite membrane prepared by the method is applied to plasma component separation, pathogenic substances in blood (the pathogenic substances depend on the types of diseases) are removed, so that an application occasion of the invention is realized, for example, severe autoimmune diseases (SAID), and by utilizing double plasma replacement therapy, pathogenic factors such as immune complexes, immune globulin and complement in plasma are directly eliminated, the cellular immune function and reticuloendothelial phagocytic function of a patient are recovered, the link of the SAID generation and development is blocked in time, and the aim of relieving the state of an illness can be achieved.
Examples 1 to 4, the hollow fiber composite membranes prepared in examples 1 to 4 were processed to prepare a hollow fiber plasma component separator having an effective membrane area of 1.0m 2 . The blood plasma is fresh anticoagulated bovine blood, and 37 deg.C bovine blood plasma
Controlling the plasma inlet flow rate to be 100ml/min, the filtrate flow rate to be 25ml/min, the waste plasma flow rate to be 5-10ml/min and the treatment time to be 3h. Membrane performance was evaluated by determining the concentration of each protein in the plasma before solution and filtration.
Clearance (%) = (1-concentration in filtrate/concentration in stock solution) × 100%
The hemolysis rate of the hollow fiber composite membrane was tested, and the immunoglobulin clearance performance of the plasma constituent separator made of the hollow fiber composite membrane was tested, the test results are shown in table 1.
TABLE 1
As can be seen from table 1, compared with example 1, the contact angles of the inner surfaces of the hollow fiber composite membranes in examples 2 to 4 are greatly reduced, which indicates that the content of the hydroxyl-terminated polyethersulfone in the separation layer of the hollow fiber composite membrane is increased, and is beneficial to improving the hydrophilic property of the inner surface of the membrane; in addition, the recalcification time of the hollow fiber composite membranes in the embodiments 2 to 4 is longer than that of the hollow fiber composite membrane in the embodiment 1, and the hemolysis rates of the hollow fiber composite membranes in the embodiments 2 to 4 are lower than that of the hollow fiber composite membrane in the embodiment 1, which shows that as the content of the hydroxyl-terminated polyethersulfone in the separation layer of the hollow fiber composite membrane increases, the hemolysis rate decreases, the recalcification time increases, and the improvement of the blood compatibility of the hollow fiber composite membrane is facilitated. Both the separation layer and the support layer of the hollow fiber composite membrane in example 4 contain hydroxyl-terminated polyethersulfone and polyethersulfone, and compared with the hollow fiber composite membranes in examples 2 and 3 in which only the separation layer contains both hydroxyl-terminated polyethersulfone and polyethersulfone, the hollow fiber composite membrane in example 4 is beneficial to further improving the blood compatibility of the whole membrane section.
The hollow fiber composite membranes of examples 1 to 4 can be used in a plasma component separator to remove various pathogenic factors such as immunoglobulin, complement, immune complex, macromolecular lipoprotein, etc. from blood, and albumin with a small molecular weight can permeate through the membrane pores and return to a patient, thereby achieving the purpose of removing harmful components from blood and treating diseases. The hollow fiber composite membranes prepared in examples 1 to 4 all show good immunoglobulin removing performance by using the hollow fiber composite membranes in examples 1 to 4, wherein the hollow fiber composite membranes prepared in example 2 show the most prominent removing performance for three immunoglobulins IgG, igM and IgA.
In order to further illustrate the present invention, the following examples are given to further illustrate the present invention. The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified; materials, reagents and the like used in examples of the present invention were commercially available unless otherwise specified.
Claims (10)
1. A preparation method of a hollow fiber composite membrane is characterized by comprising the following steps:
uniformly mixing the modified polyether sulfone mixture, the hydrophilic additive and the organic solvent to prepare a separation layer spinning solution;
uniformly mixing the modified polyether sulfone mixture, a plasticizer, a pore-forming agent and an organic solvent to prepare a supporting layer spinning solution;
forming an initial membrane by the aid of a coextrusion process through the separation layer spinning solution, the supporting layer spinning solution and the core solution, and solidifying and cleaning the initial membrane to obtain a hollow fiber composite membrane;
wherein the modified polyethersulfone mixture comprises polyethersulfone and/or hydroxylated polyethersulfone.
2. The method for preparing a hollow fiber composite membrane according to claim 1, wherein the separation layer spinning solution is prepared by the following method:
mixing 15 to 35 mass percent of modified polyether sulfone mixture, 25 to 40 mass percent of hydrophilic additive and 45 to 60 mass percent of organic solvent at the temperature of between 30 and 80 ℃ for 12 to 24 hours, and filtering and defoaming in vacuum to prepare a separation layer spinning solution.
3. The method of manufacturing a hollow fiber composite membrane according to claim 1,
the hydrophilic additive is one or the combination of two of polyethylene glycol, cellulose acetate, polyvinyl alcohol and polymethyl methacrylate;
the organic solvent is one or the combination of two of triethyl phosphate, N-methylformamide, N-dimethylacetamide and N-methylpyrrolidone.
4. The method for preparing a hollow fiber composite membrane according to claim 1, wherein the support layer spinning solution is prepared by the following method:
mixing 10 to 25 mass percent of modified polyether sulfone mixture, 5 to 30 mass percent of plasticizer, 15 to 40 mass percent of pore-forming agent and 30 to 65 mass percent of organic solvent at 30 to 80 ℃ for 12 to 24 hours, and filtering and defoaming in vacuum to prepare the supporting layer spinning solution.
5. The method of manufacturing a hollow fiber composite membrane according to claim 1,
the plasticizer is one or the combination of two of polyvinylpyrrolidone, polyethylene glycol, carboxymethyl cellulose, hydroxyethyl cellulose and polymethyl methacrylate;
the pore-foaming agent is one or the combination of two of ethanol, ethylene glycol, isopropanol, ethylene glycol monomethyl ether, diethylene glycol and glycerol;
the organic solvent is one or the combination of two of triethyl phosphate, N-methylformamide, N-dimethylacetamide and N-methylpyrrolidone.
6. The method of manufacturing a hollow fiber composite membrane according to claim 1,
the modified polyether sulfone mixture in the separation layer spinning solution comprises polyether sulfone and end-hydroxylated polyether sulfone, or the modified polyether sulfone mixture is end-hydroxylated polyether sulfone;
the modified polyether sulfone mixture in the supporting layer spinning solution comprises polyether sulfone and end-hydroxylated polyether sulfone, or the modified polyether sulfone mixture is polyether sulfone.
7. The method of preparing a hollow fiber composite membrane according to claim 1, wherein the initial membrane is prepared by:
and simultaneously extruding the separation layer spinning solution, the support layer spinning solution and the core liquid from a three-hole annular spinneret to prepare an initial membrane, wherein the three-hole annular spinneret comprises a core liquid channel, a separation layer solution channel and a support layer solution channel which are sequentially arranged from inside to outside, the core liquid is extruded from the core liquid channel, the separation layer spinning solution is extruded from the separation layer solution channel, and the support layer spinning solution is extruded from the support layer solution channel.
8. A method of preparing a hollow fibre composite membrane according to claim 1, wherein the initial membrane is coagulated by:
the initial film is sequentially solidified through an air section and a solidification bath, wherein the relative humidity of the air section is 30-90%, the temperature is 30-50 ℃, and the residence time of the initial film in the air section is 0.5-1.5 s; the coagulating bath is prepared by mixing water and a pore-forming agent, or the coagulating bath is prepared by mixing water and an organic solvent, and the liquid level of the coagulating bath is kept constant.
9. A hollow fiber composite membrane produced by the method for producing a hollow fiber composite membrane according to any one of claims 1 to 8.
10. Use of the hollow fiber composite membrane according to claim 9 in hemodialysis.
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