CN116272404A - Hollow fiber ultrafiltration membrane with symmetrical pore canal structure for hemodialysis and preparation method thereof - Google Patents

Hollow fiber ultrafiltration membrane with symmetrical pore canal structure for hemodialysis and preparation method thereof Download PDF

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CN116272404A
CN116272404A CN202310317264.9A CN202310317264A CN116272404A CN 116272404 A CN116272404 A CN 116272404A CN 202310317264 A CN202310317264 A CN 202310317264A CN 116272404 A CN116272404 A CN 116272404A
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hollow fiber
membrane
pore
pore diameter
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汪勇
应翔
邱守添
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Nanjing Tech University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • 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
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    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/16—Swelling agents
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2323/38—Graft polymerization
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    • B01D—SEPARATION
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Abstract

The invention provides a hollow fiber ultrafiltration membrane for hemodialysis, which is a porous membrane prepared by melt spinning and selective swelling by taking polysulfone-polyethylene glycol amphiphilic block copolymer as a single material, wherein the polyethylene glycol block ratio in the amphiphilic block copolymer is 30%; the pore porosity, average pore diameter and pore diameter distribution of pore channels on the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane are all in the same range, so that a symmetrical pore channel structure is formed in the thickness direction of the hollow fiber ultrafiltration membrane; the pore passages on the outer surface, the inner surface and the inner surface have the porosity of 20% -80%, the average pore diameter of 2-20 nm, and the pore diameter distribution of 2-50 nm. The hollow fiber ultrafiltration membrane has excellent scavenging performance on toxic medium molecules, high retention performance on beneficial proteins, ideal mechanical properties and no dissolution of organic components in the use process. The invention also provides a method for preparing the hollow fiber ultrafiltration membrane and a hemodialysis component taking the hollow fiber ultrafiltration membrane as a membrane wire.

Description

Hollow fiber ultrafiltration membrane with symmetrical pore canal structure for hemodialysis and preparation method thereof
Technical Field
The invention belongs to the field of separation membranes, in particular to the field of hemodialysis membranes, and particularly relates to a hollow fiber ultrafiltration membrane with a symmetrical pore structure for hemodialysis, a membrane assembly and a preparation method thereof.
Background
Hemodialysis is one of kidney replacement treatment modes of patients with acute and chronic renal failure, blood and dialysate are subjected to mass exchange inside and outside one hollow fiber through a dialyzer consisting of hollow fiber hemodialysis membranes by draining in-vivo blood to the outside, and the purposes of removing in-vivo metabolic wastes and maintaining electrolyte and acid-base balance are achieved through dispersion, ultrafiltration, adsorption and convection principles. The ideal hemodialysis membrane needs to have high safety (namely no polymer and additive are dissolved out in the use process) and good mechanical properties, and also has accurate separation performance for middle and large molecules and efficient removal performance for small molecular toxins.
The existing hemodialysis membranes can be classified into cellulose membranes and synthetic polymer membranes according to membrane-making materials. The traditional cellulose membrane has lower biocompatibility than a synthetic membrane because of a large number of hydroxyl groups and is easy to activate complement, and various complications are easy to cause in clinical use. The synthetic polymer membrane has relatively good biocompatibility and high permeability, and is the most widely used membrane material at present, wherein polysulfone and polyethersulfone are the most clinically used.
At present, the preparation of the hollow fiber hemodialysis membrane is mainly carried out by a solution spinning method (NIPS), wherein a solution of polysulfone and polyether sulfone is immersed in a non-solvent coagulating bath, the non-solvent in the coagulating bath is diffused into a casting solution, and the solvent is diffused from the casting solution to the coagulating bath, so that a polymer is rapidly separated out from the casting solution from top to bottom, and the hollow fiber membrane is obtained. The solution spinning method is the most commonly used method in the industry at present because the obtained film has high pore rate and can be prepared in a large scale. However, the solution spinning method can generate a large amount of organic waste liquid and waste water in the production and preparation process, so as to pollute the environment; more importantly, the hollow fiber membrane prepared by the method is of a typical asymmetric structure and cannot meet the actual requirements of hemodialysis. Because in this typical asymmetric structure, the inner and outer surfaces of the membrane are generally porous structures with pore diameters of several to several tens of nanometers, while the interior of the membrane is a finger-like macropore with pore diameters of several tens of micrometers or even up to hundreds of micrometers. Although the nano-scale pore canal on the surface plays a role in separation, the finger-shaped macropores in the inner part can ensure that the whole membrane has higher flux, the hollow fiber membrane has the characteristics of larger size of the inner pore canal, overlarge size difference between the inner pore canal and the surface pore canal, poor uniformity of the size of the inner surface pore canal and the outer surface pore canal, and the like, so that the hollow fiber membrane has poor capability of removing the medium-large molecular protein toxin. And the asymmetric structure generally has the defects of poor mechanical property, easiness in damaging a thinner effective separation layer and the like. In addition, polysulfone materials are highly hydrophobic and, when used as a hemodialysis membrane material, they generally require surface modification to meet the requirements for hemodialysis. The modification method comprises chemical grafting modification and blending modification, wherein the former method is complex and has low economic benefit; the latter can gradually run off when the hydrophilic additive is subjected to wall shear force or post sterilization treatment in use, so that the performance of the film is reduced, and even dissolution of the additive can occur to cause complement activation and complications of patients.
Therefore, development of a novel hemodialysis membrane which has accurate separation capability on middle and large molecules in blood, stable performance and simple preparation method is needed to better meet the hemodialysis requirement and is suitable for industrial production.
Disclosure of Invention
The invention aims at: the hollow fiber ultrafiltration membrane is more suitable for hemodialysis, has excellent scavenging performance on toxic medium molecules and high retention performance on beneficial proteins due to the symmetrical pore canal structure in the thickness direction, has a thicker effective separation layer and ideal mechanical property, does not need surface modification, and does not have organic components dissolved out in the use process.
Another object of the invention is: the method for preparing the hollow fiber ultrafiltration membrane for hemodialysis is provided, so that the hollow fiber ultrafiltration membrane has a symmetrical pore structure in the thickness direction, and the obtained pore structure has small pore diameter and narrow pore diameter distribution.
The above object of the present invention is achieved by the following means:
in a first aspect, the invention provides a hollow fiber ultrafiltration membrane for hemodialysis, which is a porous membrane prepared by melt spinning and selective swelling by taking a polysulfone-polyethylene glycol amphiphilic block copolymer as a single material, wherein the polyethylene glycol block ratio in the amphiphilic block copolymer is 30%; the pore canal of the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane have similar structural characteristics, namely the porosity, the average pore diameter and the pore diameter distribution are all in the same range, thereby forming a symmetrical pore canal structure in the thickness direction.
In the preferred scheme of the invention, pore passages on the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane have porosities within the range of 10% -80%, average pore diameters within the range of 2 nm-20nm, and pore diameter distribution within the range of 2 nm-50 nm.
In a further preferred scheme of the invention, pore passages on the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane have porosities within a range of 10% -70%, average pore diameters within a range of 2 nm-20nm, and pore diameter distribution within a range of 2 nm-25 nm.
In a still further preferred scheme of the invention, pore passages on the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane have porosities within a range of 10% -65%, average pore diameters within a range of 3 nm-12 nm, and pore diameter distribution within a range of 2nm-15 nm.
In a more preferable scheme of the invention, the porosity of the outer surface pore canal is 10% -40%, the average pore diameter is 2 nm-10nm, and the pore diameter distribution is 2nm-15nm; the pore canal on the inner surface has the porosity of 10% -40%, the average pore diameter of 2-10 nm and the pore diameter distribution of 2-20 nm; the porosity of the inner pore canal of the membrane is 40% -70%, the average pore diameter is 5-20 nm, and the pore diameter distribution is 2-25 nm.
In the most preferred scheme of the invention, the porosity of the outer surface pore canal is 15-30%, the average pore diameter is 3-6 nm, and the pore diameter distribution is 2-8 nm; the pore canal on the inner surface has the porosity of 10% -25%, the average pore diameter of 4-8 nm and the pore diameter distribution of 2-12 nm; the porosity of the inner pore canal of the membrane is 55% -65%, the average pore diameter is 8-12 nm, and the pore diameter distribution is 2-15 nm.
In a second aspect, the present invention provides a hemodialysis membrane module comprising the hollow fiber ultrafiltration membrane as a membrane filament.
In a third aspect, the present invention also provides a method for preparing the hollow fiber ultrafiltration membrane for hemodialysis, comprising:
1) Preparing a hollow fiber by melt spinning a polysulfone-polyethylene glycol block copolymer, wherein the polyethylene glycol block ratio of the polysulfone-polyethylene glycol block copolymer is 30%;
2) Immersing the hollow fiber obtained in the step 1) in a mixed solvent (20 wt% of acetone and 80wt% of n-propanol), carrying out selective swelling treatment for 0.5-3 h at 60-65 ℃, transferring into n-heptane for treatment for 5min, and drying to obtain the hollow fiber ultrafiltration membrane with a symmetrical pore structure for hemodialysis.
In the preferred method of the present invention, the swelling treatment of 2) is carried out at 65℃for 1 hour.
In the preferred method of the present invention, the swelling treatment of 2) uses a microwave treatment with a power of 160-800W for 15-60s.
In the prior art, in early researches for preparing hollow fiber porous membranes by utilizing selective swelling, the inventor groups have realized the regulation of pore channel structures and performances by regulating factors such as the composition of a swelling agent, the swelling temperature and the time of the selective swelling. However, the hollow fiber porous membrane obtained by the above-mentioned regulation scheme only obtains a certain degree of improvement on water flux, and the requirements for removing small molecular impurities and simultaneously removing toxic medium molecules and intercepting beneficial macromolecular proteins in hemodialysis are difficult to meet all the time. Particularly, the clearance rate of molecular toxins in beta 2-microglobulin, myoglobin and the like is too low, so that the therapeutic effect in hemodialysis is not ideal. The inventors have conducted intensive studies to analyze the relationship between the unique performance requirements of hemodialysis membranes and the pore structure characteristics of porous membranes, and based on the relationship, a large number of hollow fiber membrane pore-forming screening experiments are conducted, wherein the experiments comprise breaking the conventional thought of adjusting selective swelling conditions, in turn, screening hydrophilic block ratios in amphiphilic block copolymers, and finally, under specific selective swelling conditions, finding that the polyethylene glycol block ratios in polysulfone-polyethylene glycol block copolymers are 30%, under the condition that the polyethylene glycol block ratios in the polysulfone-polyethylene glycol block copolymers can be prepared by using a melt spinning and selective swelling method, hollow fiber ultrafiltration membranes with symmetrical pore structures in the thickness direction are prepared, and the pore structures of the inner surface and the outer surface of the membrane and the inner surface of the membrane are respectively provided with nano-scale bicontinuous pore structures between 2 and 50nm, namely, the pore structures of the inner surface and the outer surface of the membrane are almost completely consistent, and the pore sizes of the inner surface of the membrane are slightly smaller than the inner part due to enrichment of hydrophilic blocks on the surface. Compared with the existing various hollow fiber porous membranes, the hollow fiber membrane provided by the invention has a symmetrical pore structure which is a special structure, not only brings higher mechanical property and flux for the hollow fiber membrane, but also has accurate separation property, has higher clearance rate for medium molecular toxins and small molecular impurities in blood, almost does not cause beneficial protein loss, and is obviously superior to the condition that polyethylene glycol exists in other block ratios in the performances of BSA interception rate, lysozyme clearance rate, myoglobin clearance rate and the like (see figure 18). And the hollow fiber ultrafiltration membrane has relatively consistent structure of inner and outer pore channels, so that the hollow fiber ultrafiltration membrane hardly suffers damage in the hemodialysis use process, thereby causing the reduction of separation performance.
In addition, the solution spinning method (NIPS) commonly used at present often needs to be modified due to the problem of high hydrophobicity of polysulfone materials, and the modification method comprises chemical grafting modification and blending modification. The former method is complex and has low economic benefit; the hydrophilic agent is gradually lost when the hydrophilic agent is subjected to wall shearing force or post-sterilization treatment in use, so that the performance is reduced, even the dissolution of the additive occurs to cause complement activation, and complications of patients are caused; in addition, the hollow fiber membrane obtained by the NIPS method is usually provided with a nanoscale pore canal with smaller pore diameter only at the outer surface, so that the separation of macromolecules in blood can be realized, and the finger-shaped macropores with the inner microscale pore diameter have no separation capability on the macromolecules in blood, so that the actual separation layer is only a very thin layer at the inner surface and the outer surface, and the thickness of the separation layer is not more than 10 mu m. Such thin separation layers, coupled with the internal micro-scale macroporous structure, mean poor mechanical strength, and practice has shown that such separation membranes are prone to wear in hemodialysis applications, which results in excessive treatment costs for dialysis patients. Compared with the method, the hollow fiber ultrafiltration membrane is prepared from a single material, and complicated additional modification is not needed, so that the process cost can be obviously reduced. It is more worth mentioning that the hollow fiber membrane of the invention can be swelled to obtain larger thickness under specific block proportion, so that the nano-scale pore canal with the pore diameter ranging from 2nm to 50nm is uniformly distributed in the whole thickness range from the outer surface to the inner surface of the hemodialysis membrane, thus the pore canal structure in the whole thickness range can play a role of precisely and effectively separating medium and macromolecules, the actual separation layer thickness of the hollow fiber membrane can reach 100-200 mu m, and the mechanical property and the service life of the hollow fiber membrane prepared by NIPS method are surprisingly improved, thereby greatly reducing the treatment cost of dialysis patients. It can be seen that the present invention provides a significant improvement over NIPS, both in terms of manufacturing process and in terms of performance.
Moreover, for hemodialysis industry, the preparation method of the hollow fiber ultrafiltration membrane is simple and convenient, easy to operate and low in cost, does not involve a complex membrane surface modification process, and has good amplified preparation and practical application prospects. The membranes with certain specific structures and polymer block proportions prepared by the method can be widely applied to the fields of blood perfusion and the like.
Drawings
FIG. 1 is an SEM image of the outer surface of a hemodialysis membrane obtained in example 2.
FIG. 2 is an SEM image of the inner surface of a hemodialysis membrane obtained in example 2.
FIG. 3 is an SEM image of the outer cross section of the hemodialysis membrane obtained in example 2.
FIG. 4 is a SEM image of a cross section of a hemodialysis membrane obtained in example 2.
FIG. 5 is an SEM image of the inner side cross section of the hemodialysis membrane obtained in example 2.
FIG. 6 is a low-magnification SEM image of the cross section of a hemodialysis membrane obtained in example 2.
FIG. 7 is a graph of toxin clearance performance of the hemodialysis cartridge obtained in example 2.
FIG. 8 is a graph showing the comparison of the performance of the hemodialysis unit obtained in example 2 with other types of performance.
FIG. 9 is a graph comparing the performance of hemodialysis assemblies obtained in example 1, example 2, example 3, and example 4.
FIG. 10 is a graph comparing the performance of hemodialysis assemblies obtained in example 2, example 5, and example 6.
FIG. 11 is an SEM image of the outer surface of the hemodialysis membrane obtained in comparative example 1.
FIG. 12 is an SEM image of the inner surface of a hemodialysis membrane obtained in comparative example 1.
Fig. 13 is a cross-sectional SEM image of the hemodialysis membrane obtained in comparative example 1.
FIG. 14 is an SEM image of the outer surface of a hemodialysis membrane obtained in comparative example 2.
FIG. 15 is an SEM image of the inner surface of a hemodialysis membrane obtained in comparative example 2.
FIG. 16 is a SEM image of the cross-section of a hemodialysis membrane obtained in comparative example 2.
FIG. 17 is a cross-sectional SEM image of an asymmetric hemodialysis membrane obtained by NIPS method in comparative example 3.
FIG. 18 is a graph showing the comparison of the performance of hemodialysis assemblies obtained in example 2, comparative example 1, comparative example 2, and comparative example 3.
Detailed Description
The invention provides a hollow fiber ultrafiltration membrane for hemodialysis, which is a porous membrane prepared by melt spinning and selective swelling by taking polysulfone-polyethylene glycol amphiphilic block copolymer as a single material, wherein the polyethylene glycol block ratio in the amphiphilic block copolymer is 30%; the pore canal of the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane have similar structural characteristics, namely the porosity, the average pore diameter and the pore diameter distribution are all in the same range, thereby forming a symmetrical pore canal structure in the thickness direction.
The hollow fiber ultrafiltration membrane provided by the invention is further used as a membrane wire to prepare a hemodialysis component, and the method comprises the following steps: the hollow fiber ultrafiltration membrane disclosed by the invention is folded, sterilized and disinfected, a certain number of membrane wires are placed in a dialyser shell according to the required membrane area, and the two ends of the membrane wires are sealed by polyurethane and epoxy resin glue, so that only the inside of the membrane wires can pass through liquid while other positions are free from defects, and the hemodialysis component is obtained after the membrane wires are placed for one day at normal temperature. The sterilization process is not particularly limited, and various methods including ethylene oxide, hydrogen peroxide or high temperature sterilization can be used. The proper disinfection and sterilization method can be selected according to the specific use environment and conditions.
Experiments prove that the hemodialysis component prepared based on the hollow fiber ultrafiltration membrane provided by the invention can maintain the clearance rate of about 50% -70% for macromolecular toxins and the clearance rate of up to 95% for micromolecular toxins on the premise of 99.9% interception for macromolecular proteins.
The invention is further explained below with reference to examples. The following examples are given only to illustrate the invention, wherein the modules have a membrane area of 0.1 to 1.5m 2 But are not intended to limit the scope of the invention.
Example 1
PSF is carried out 35 -PEG 30 -PSF 35 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a 65 ℃ water bath for 0.5 h, and then transferred into n-heptane for 5min. And taking out the hollow fiber immediately after the treatment is finished, and drying at 40 ℃ to obtain the symmetrical porous hollow fiber membrane with continuous open pores. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has the porosity of 35.1 percent, the average pore diameter of 5.5nm and the pore diameter distribution of 3nm-8nm; pore canal on the inner surface has a porosity of 21.3%, an average pore diameter of 7.5nm, and pore diameter distribution of 5-10 nm; the pore canal inside the membrane has the porosity of 46.4%, the average pore diameter of 10.3nm and the pore diameter distribution of 2nm-15 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained middle partThe hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends of the hollow fiber membrane, and the membrane is obtained after one day of standing at normal temperature, and the membrane area is 0.2m 2 Is provided.
Hemodialysis testing was performed using the hemodialysis cartridge prepared in this example, as follows:
a mixture of urea (1.5 g/L) and lysozyme (0.2 g/L) and BSA (1 g/L) were used as simulated blood, and a PBS solution was used as simulated dialysate. During dialysis, the simulated blood and simulated dialysate pass through the dialysis membrane module in opposite directions at speeds of 200 and 500 mL/min, respectively. After dialysis for 4 hours, 20mL of test solution was taken from the simulated blood outlet for analysis.
The test results show that the ultrafiltration coefficient of the hemodialysis membrane module prepared in the embodiment is 14.3 mL/(h.mmHg), the BSA interception is 98.7%, the lysozyme clearance is 39.0%, and the myoglobin clearance is 33.2%.
Example 2
Hemodialysis membranes were prepared as described in reference to example 1, with the following protocol, varying the swelling time:
PSF is carried out 35 -PEG 30 -PSF 35 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a 65 ℃ water bath for 1h, and then transferred into n-heptane for 5min. And taking out the hollow fiber immediately after the treatment is finished, and drying at 40 ℃ to obtain the symmetrical porous hollow fiber membrane with continuous open pores. The hollow fiber membrane was observed under an electron microscope, and the results are shown in FIGS. 1 to 6. Fig. 1, 2, 3, 4, 5 and 6 are SEM images of the outer surface, inner surface, outer cross section, inner cross section, and low-magnification cross section, respectively, of the hemodialysis membrane prepared in this example. As can be seen from the figure: under the condition that the polyethylene glycol block ratio is 30%, the hollow fiber hemodialysis membrane prepared by the polysulfone-polyethylene glycol block copolymer through melt spinning and selective swelling has basically consistent pore structure characteristics of the inner surface and the outer surface, uniform pore openings of the outer surface and the inner surface, smaller pore channel sizes in all positions and high porosity. So that it divides the large and mediumThe sieving effect of the sub-toxins is good. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has the porosity of 15.7%, the average pore diameter of 6.1nm and the pore diameter distribution of 2nm-8nm; pore canal on the inner surface has porosity of 22.4%, average pore diameter of 7.8nm and pore diameter distribution of 3-12 nm; the pore canal inside the membrane has the porosity of 61.8%, the average pore diameter of 10.8nm and the pore diameter distribution of 3 nm-15 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends, and the membrane area is 0.2m after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis test was performed using the hemodialysis module prepared in this example, and the test method was the same as in example 1, and the test result showed that the ultrafiltration coefficient of the hemodialysis membrane module prepared in this example was 25.4 mL/(h.mmhg), the BSA rejection was 99.9%, the lysozyme clearance was 69.2%, and the myoglobin clearance was 49.8%. As shown in FIG. 7, the hemodialysis membrane module prepared by the embodiment also has ideal clearance rate for other small and medium molecular toxins. The applicant also conducted comparative analysis of the test results of this example with experimental data described in the prior art, and the results are shown in fig. 8. The test results of This example are represented by the "This work" labeled with a five-star shape in fig. 8, and it can be seen that the hollow fiber membrane of This example is superior to other various types of existing hemodialysis membranes in both BSA rejection rate and lysozyme removal rate.
Example 3
A hollow fiber membrane was prepared by the method described in example 1, with the following specific scheme, by varying the swelling time:
PSF is carried out 35 -PEG 30 -PSF 35 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a 65 ℃ water bath for 2 hours, and then transferred into n-heptane for 5 minutes. Immediately after the treatment, the hollow fiber is taken out and dried at 40 ℃ to obtain the symmetrical multi-hole continuous openingA porous hollow fiber membrane. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has the porosity of 23.7%, the average pore diameter of 7.1nm and the pore diameter distribution of 3nm-10nm; pore canal on the inner surface has a porosity of 23.9%, an average pore diameter of 7.8nm and pore diameter distribution of 2nm-15nm; the pore canal inside the membrane has the porosity of 63.2%, the average pore diameter of 12.1nm and the pore diameter distribution of 5nm-20 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends, and the membrane area is 0.2m after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis test was performed using the hemodialysis module prepared in this example, and the test method was the same as in example 1, and the test results showed that the ultrafiltration coefficient of the hemodialysis membrane module prepared in this example was 26.1 mL/(h.mmHg), the BSA retention was 99.9%, the lysozyme clearance was 39.2%, and the myoglobin clearance was 40.4%.
Example 4
A hollow fiber membrane was prepared by the method described in example 1, with the following specific scheme, by varying the swelling time:
PSF is carried out 35 -PEG 30 -PSF 35 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a water bath at 65℃for 3h, and then transferred into n-heptane for 5 minutes. And taking out the hollow fiber immediately after the treatment is finished, and drying at 40 ℃ to obtain the symmetrical porous hollow fiber membrane with continuous open pores. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has the porosity of 28.6 percent, the average pore diameter of 7.5nm and the pore diameter distribution of 3nm-13nm; the pore canal on the inner surface has the porosity of 34.9%, the average pore diameter of 7.7nm and the pore diameter distribution of 5 nm-10nm; the pore canal inside the membrane has the porosity of 46.4%, the average pore diameter of 13.3nm and the pore diameter distribution of 5 nm-22 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained product is then processedThe hollow fiber membrane of (2) is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends of the membrane, and the membrane with the area of 0.2m is obtained after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis test was performed using the hemodialysis module prepared in this example, and the test method was the same as in example 1, and the test results showed that the ultrafiltration coefficient of the hemodialysis membrane module prepared in this example was 27.1 mL/(h.mmHg), the BSA retention was 99.9%, the lysozyme clearance was 38.0%, and the myoglobin clearance was 22.4%. Comparing the performance of the hemodialysis module of example 1, example 2, example 3 and example 4, and referring to fig. 9, it is apparent from fig. 9 that the removal effect of the molecular toxins in both lysozyme and myoglobin is optimal and the ultrafiltration coefficient is substantially consistent with the BSA interception at a swelling time of 1h.
Example 5
A hollow fiber membrane was prepared by the method described in example 1, with the following specific scheme by changing the swelling temperature:
PSF is carried out 35 -PEG 30 -PSF 35 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a 55 ℃ water bath for 1h, and then transferred into n-heptane for 5min. And taking out the hollow fiber immediately after the treatment is finished, and drying at 40 ℃ to obtain the symmetrical porous hollow fiber membrane with continuous open pores. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has the porosity of 10.1 percent, the average pore diameter of 6.2nm and the pore diameter distribution of 2nm-9nm; pore canal on the inner surface has porosity of 22.0%, average pore diameter of 7.1nm and pore diameter distribution of 5 nm-12 nm; the pore canal inside the membrane has the porosity of 42.2%, the average pore diameter of 10.3nm and the pore diameter distribution of 3 nm-18 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends, and the membrane area is 0.2m after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis test was performed using the hemodialysis module prepared in this example, and the test method was the same as in example 1, and the test result showed that the ultrafiltration coefficient of the hemodialysis membrane module prepared in this example was 17.1 mL/(h.mmhg), the BSA rejection was 99.8%, the lysozyme clearance was 39.8%, and the myoglobin clearance was 24.9%.
Example 6
A hollow fiber membrane was prepared by the method described in example 1, with the following specific scheme by changing the swelling temperature:
PSF is carried out 35 -PEG 30 -PSF 35 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a 60 ℃ water bath for 1 hour, and then transferred into n-heptane for 5 minutes. And taking out the hollow fiber immediately after the treatment is finished, and drying at 40 ℃ to obtain the symmetrical porous hollow fiber membrane with continuous open pores. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has the porosity of 11.9%, the average pore diameter of 7.5nm and the pore diameter distribution of 2nm-11nm; pore canal on the inner surface has porosity of 30.9%, average pore diameter of 8.1nm and pore diameter distribution of 5-12 nm; the pore canal inside the membrane has a porosity of 47.4%, an average pore diameter of 11.0nm and pore diameter distribution of 2 nm-20 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends, and the membrane area is 0.2m after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis module prepared in this example was used for hemodialysis test, and the test method was the same as in example 1, and the test result showed that the ultrafiltration coefficient of the hemodialysis membrane module prepared in this example was 20.1 mL/(h.mmhg), the BSA retention was 99.9%, the lysozyme clearance was 42.8%, and the myoglobin clearance was 35%. Comparing the performance of the hemodialysis module of example 2, example 5, and example 6, the results are shown in fig. 10, and it is apparent from fig. 10 that the removal effect of the molecular toxins in both lysozyme and myoglobin is optimal and the ultrafiltration coefficient thereof is also optimal at a swelling temperature of 65 ℃.
Example 7
A hollow fiber membrane was prepared by the method described in example 1, with the following specific scheme by changing the swelling temperature:
PSF is carried out 30 -PEG 25 -PSF 30 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a 55 ℃ water bath for 1h, and then transferred into n-heptane for 5min. And taking out the hollow fiber immediately after the treatment is finished, and drying at 40 ℃ to obtain the symmetrical porous hollow fiber membrane with continuous open pores. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has a porosity of 31.3%, an average pore diameter of 12.1nm and pore diameter distribution of 5nm-20nm; pore canal on the inner surface has porosity of 35.3%, average pore diameter of 12.6nm and pore diameter distribution of 2-18 nm; the pore canal inside the membrane has the porosity of 60.3%, the average pore diameter of 15.8nm and the pore diameter distribution of 2 nm-22 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends, and the membrane area is 0.2m after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis test was performed using the hemodialysis module prepared in this example, and the test method was the same as in example 1, and the test result showed that the ultrafiltration coefficient of the hemodialysis membrane module prepared in this example was 40.3 mL/(h.mmhg), the BSA retention was 95.3%, the lysozyme clearance was 45.5%, and the myoglobin clearance was 39.8%.
Example 8
Hemodialysis membranes were prepared as described in reference to example 1, with the following protocol, varying the swelling time:
PSF is carried out 35 -PEG 30 -PSF 35 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone +80wt% n-propyl)Alcohol), treated in a 65 ℃ water bath for 1h, then transferred to n-heptane for 5min. And taking out the hollow fiber immediately after the treatment is finished, and drying at 40 ℃ to obtain the symmetrical porous hollow fiber membrane with continuous open pores. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has the porosity of 15.7%, the average pore diameter of 6.1nm and the pore diameter distribution of 2nm-8nm; pore canal on the inner surface has porosity of 22.4%, average pore diameter of 7.8nm and pore diameter distribution of 3-12 nm; the pore canal inside the membrane has the porosity of 61.8%, the average pore diameter of 10.8nm and the pore diameter distribution of 3 nm-15 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends, and the membrane area is 1.5m after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis test was performed using the hemodialysis module prepared in this example, and the test method was the same as in example 1, and the test results showed that the ultrafiltration coefficient of the hemodialysis membrane module was 28.9 mL/(h.mmHg), the BSA rejection was 99.9%, the lysozyme clearance was 69.8%, and the myoglobin clearance was 50.1%. In this example, the membrane area of the hemodialysis module was set to 0.2m as compared with example 2 2 Expanded to 1.5m 2 Experimental results demonstrate that the dialysis performance of the hemodialysis module does not decrease, or even improves, with the expansion of the membrane area.
Comparative example 1
A hollow fiber membrane was prepared by the method described in example 1, with the following specific scheme, by varying the polymer block ratio:
PSF is carried out 40 -PEG 20 -PSF 40 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the obtained hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a 65 ℃ water bath for 1h, and then transferred into n-heptane for 5min. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃. The hollow fiber porous membrane was observed under an electron microscope, and the results are shown in FIGS. 11 to 13Shown. FIGS. 11, 12 and 13 are SEM images of the outer surface, inner surface and cross section of a hemodialysis membrane prepared under the conditions of this comparative example, respectively, and it is also apparent that the block has a larger pore size distribution range than that of the membrane prepared under the conditions of comparative example 2. And measuring the structural parameters of the membrane pore canal to obtain: the pore canal of the outer surface of the hollow fiber membrane has the porosity of 25.4 percent, the average pore diameter of 7.1nm and the pore diameter distribution of 6nm-25nm; pore canal on the inner surface has porosity of 30.0%, average pore diameter of 8.8nm and pore diameter distribution of 3-19 nm; the pore canal inside the membrane has a porosity of 59.2%, an average pore diameter of 20.8nm and pore diameter distribution of 5 nm-30 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends, and the membrane area is 0.2m after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis test was performed using the hemodialysis module prepared in this comparative example, and the test method was the same as in example 1, and the test result showed that the ultrafiltration coefficient of the hemodialysis membrane module prepared in this example was 36.0 mL/(h.mmhg), the BSA rejection was 95.6%, the lysozyme clearance was 34.2%, and the myoglobin clearance was 22.2%.
In the hemodialysis test of the comparative example, the pore size distribution of the membrane is wider, and because BSA is used as a protein with the long axis of 14.1nm, lysozyme is used as an elliptical protein with the long axis of 4.5nm and the short axis of 3.0nm, the lysozyme is easily trapped by the membrane prepared in the comparative example in the dialysis process, so that the test result shows a larger ultrafiltration coefficient and lower toxin clearance rate.
Comparative example 2
A hollow fiber membrane was prepared by the method described in example 1, with the following specific scheme, by varying the polymer block ratio:
PSF is carried out 30 -PEG 40 -PSF 30 The block copolymer was fed into a twin screw extruder and extruded through a spinneret, and the resulting hollow fiber was immersed in a mixed solvent (20 wt% acetone+80 wt% n-propanol), treated in a 65℃water bath for 1h, and then transferred into n-heptaneTreating for 5min. And taking out the hollow fiber immediately after the treatment is finished, and drying at 40 ℃ to obtain the symmetrical porous hollow fiber membrane with continuous open pores. The hollow fiber porous membrane was observed under an electron microscope, and the results are shown in fig. 14 to 16. FIGS. 14, 15 and 16 are SEM images of the outer surface, inner surface and cross section of a hemodialysis membrane prepared under the conditions of this comparative example, respectively, in which it is evident that the blocks have substantially larger channels and more dense areas than the membrane prepared under the conditions of comparative example 2. And measuring the structural parameters of the membrane pore canal to obtain: the outer surface of the hollow fiber membrane is substantially free of visible channels; pore canal on the inner surface has porosity of 7.8%, average pore diameter of 5.5nm and pore diameter distribution of 1 nm-21 nm; the pore canal inside the membrane has the porosity of 34.2%, the average pore diameter of 22.4nm and the pore diameter distribution of 5 nm-30 nm.
The hollow fiber membrane is used as membrane yarn to prepare a hemodialysis component, and the specific method is as follows: the obtained hollow fiber membrane is folded and placed in a dialyser shell, polyurethane and epoxy resin are used for sealing the two ends, and the membrane area is 0.2m after the membrane is placed for one day at normal temperature 2 Is provided.
The hemodialysis test was performed using the hemodialysis module prepared in this comparative example, and the test method was the same as in example 1, and the test result showed that the ultrafiltration coefficient of the membrane module prepared in this comparative example was 19.4 mL/(h.mmHg), the BSA retention was 99.9%, the lysozyme clearance was only 4.2%, and the myoglobin clearance was only 2.0%.
In the hemodialysis test of this comparative example, the dialysis module has a certain ultrafiltration coefficient due to a large pore size distribution, but basically less toxin molecules pass through the membrane pores due to low porosity, so that it has a low toxin clearance rate.
Comparative example 3
The asymmetric hemodialysis membrane is prepared by a NIPS method, and the specific scheme is as follows:
PSF is carried out 40 -PEG 20 -PSF 40 Dissolving with N-methyl-2-pyrrolidone (NMP) at 60deg.C to obtain PSF with mass fraction of 17-25 wt%b-PEG casting solution. Subsequently, PSF-bPEG casting solutionThe mixture was degassed 12 h in a forced air oven and cooled to room temperature. PSF of about 5 mLbPouring the PEG casting solution onto a clean glass plate, and uniformly scraping with a scraper with the height of 300 mu m to obtain PSF-b-PEG liquid film. After 10% s in air, PSF was obtainedbThe PEG liquid film is wholly immersed in the deionized water coagulation bath to cause the liquid film to be subjected to phase separation. After about 10 min, PSF-bThe PEG film spontaneously breaks off from the glass plate, which is removed, rinsed with deionized water to remove residual solvent, and the film is stored in deionized water.
FIG. 17 is a SEM image of a cross section of an asymmetric hemodialysis membrane prepared by the NIPS method, wherein the upper layer is a small round hole, and the lower layer is a large finger hole, thus resulting in a larger ultrafiltration coefficient, but more macromolecular proteins are lost from the large holes under the condition of lower clearance of lysozyme due to too wide pore size distribution.
The membrane pore channel structure parameters of the hemodialysis hollow fiber membrane prepared in the example are as follows: the thickness of the separation layer of the hollow fiber membrane is 300-1400nm, the porosity is 15.0%, the average pore diameter is 6.1nm, and the pore diameter distribution is 3-9.4 nm; the internal finger pore porosity was 62.1%, the average pore diameter was 7 μm, and the pore size distribution was 5 μm to 20 μm. The ultrafiltration coefficient was 100.2 mL/(h.mmHg), the BSA retention was 93.2%, and the lysozyme clearance was 36.3%.

Claims (9)

1. A hollow fiber ultrafiltration membrane for hemodialysis is a porous membrane prepared by taking polysulfone-polyethylene glycol amphiphilic block copolymer as a single material and carrying out melt spinning and selective swelling, and is characterized in that: in the amphiphilic block copolymer, the polyethylene glycol block ratio is 30%; the pore porosity, average pore diameter and pore diameter distribution of pore channels on the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane are all in the same range, so that a symmetrical pore channel structure is formed in the thickness direction of the hollow fiber ultrafiltration membrane; the pore passages on the outer surface, the inner surface and the inner surface have porosities of 10% -80%, average pore diameters of 2-20 nm and pore diameter distribution of 2-50 nm.
2. The hollow fiber ultrafiltration membrane of claim 1 wherein: the pore passages on the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane have porosities within the range of 10% -70%, average pore diameters within the range of 2 nm-20nm, and pore diameter distribution within the range of 2 nm-25 nm.
3. The hollow fiber ultrafiltration membrane of claim 1 wherein: the pore passages on the outer surface, the inner surface and the inner surface of the hollow fiber ultrafiltration membrane have porosities within the range of 10% -65%, average pore diameters within the range of 3 nm-12 nm, and pore diameter distribution within the range of 2nm-15 nm.
4. The hollow fiber ultrafiltration membrane of claim 1 wherein: the porosity of the outer surface pore canal is 10-40%, the average pore diameter is 2-10 nm, and the pore diameter distribution is 2-15 nm; the pore canal on the inner surface has the porosity of 10% -40%, the average pore diameter of 2-10 nm and the pore diameter distribution of 2-20 nm; the porosity of the inner pore canal of the membrane is 40% -70%, the average pore diameter is 5-20 nm, and the pore diameter distribution is 2-25 nm.
5. The hollow fiber ultrafiltration membrane of claim 1 wherein: the pore canal of the outer surface has the porosity of 15-30%, the average pore diameter of 3-6 nm and the pore diameter distribution of 2-8 nm; the pore canal on the inner surface has the porosity of 10% -25%, the average pore diameter of 4-8 nm and the pore diameter distribution of 2-12 nm; the porosity of the inner pore canal of the membrane is 55% -65%, the average pore diameter is 8-12 nm, and the pore diameter distribution is 2-15 nm.
6. A hemodialysis membrane module comprising the hollow fiber ultrafiltration membrane for hemodialysis according to claim 1 as a membrane filament.
7. A method for preparing the hollow fiber ultrafiltration membrane for hemodialysis according to claim 1, comprising:
1) Preparing a hollow fiber by melt spinning a polysulfone-polyethylene glycol block copolymer, wherein the polyethylene glycol block ratio of the polysulfone-polyethylene glycol block copolymer is 30%;
2) Immersing the hollow fiber obtained in the step 1) in a mixed solvent containing 20wt% of acetone and 80wt% of n-propanol, carrying out selective swelling treatment for 0.5-3 h at 60-65 ℃, transferring into n-heptane for treatment for 5min, and drying to obtain the hollow fiber ultrafiltration membrane with a symmetrical pore structure for hemodialysis.
8. The method of claim 7, wherein: 2) The swelling treatment is carried out at 65 ℃ for 1h.
9. The method of claim 7, wherein: 2) The swelling treatment process uses 160-800W microwave treatment for 15-60s.
CN202310317264.9A 2023-03-29 2023-03-29 Hollow fiber ultrafiltration membrane with symmetrical pore canal structure for hemodialysis and preparation method thereof Pending CN116272404A (en)

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