Preparation of anticoagulation hollow fiber membrane by core liquid modification method and its application

Abstract

The present invention discloses a core liquid modification method for preparing an anticoagulation hollow fiber membrane and its application. The anticoagulation hollow fiber membrane comprises a hydrophobic hollow fiber membrane and a modified high molecular polymer formed on the inner surface of the hollow fiber membrane, and the modified high molecular polymer is represented by the following formula: #imgabs0# wherein R1 is a reinforcing carbon chain segment containing a hydrophobic group, R2 is a cross-linked carbon chain segment containing siloxane, and R3 is an anticoagulation carbon chain segment containing a sulfonic acid group or a carboxylic acid group; the number of carbons in the carbon chain segment is 1-200, and x, y, and z are positive integers. The anticoagulation hollow fiber membrane provided by the present invention achieves excellent anticoagulation effect while maintaining excellent ultrafiltration performance.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer membranes, and more specifically, relates to a core liquid modification method for preparing an anticoagulation hollow fiber membrane and application thereof. Background Art

[0002] Because of kidney damage, patients with end-stage renal disease (ESRD) are unable to excrete toxins and excess water from the body and need to undergo hemodialysis. The polymer dialysis membrane material used in the hemodialysis process is a foreign substance relative to the human body. During the dialysis process, it is easy to adhere to proteins, thereby triggering the coagulation cascade effect, forming blood scabs on the membrane surface, affecting the size of the membrane pores, and thus reducing the dialysis efficiency. At present, there is a method of pre-filling the pipeline with anticoagulants and injecting heparin to block the activation of coagulation factors, thereby interrupting the occurrence of the coagulation cascade reaction. However, heparin may cause allergic reactions in the human body, and patients will experience symptoms such as vomiting and dizziness. In addition, while heparin reduces the activity of thrombin in the blood, it will inhibit the adhesion and aggregation of platelets, which is prone to spontaneous bleeding. For patients with bleeding diseases, the use of heparin is extremely dangerous.

[0003] Anticoagulant modification of dialyzers with synthetic heparin is an effective method to reduce the abuse of heparin. The anticoagulant modification methods can be divided into pre-modification and post-modification. Pre-modification is to add the modification liquid to the casting liquid and prepare the modified hemodialysis membrane by spinning. In patent CN 110756066A, it is disclosed that sulfonated citric acid chitosan is added to polyether sulfone as a membrane material, and a sulfonated citric acid chitosan modified polysulfone hemodialysis membrane with good biocompatibility is prepared by dry-wet spinning. The modified polysulfone hollow fiber membrane has excellent hydrophilicity, and its anti-protein adsorption ability and anti-coagulation performance are effectively improved. The bovine serum protein adsorption amount is increased from 393μg / cm 2 Down to 54 μg / cm 2 , the hemolysis rate decreased from 2.7% to 1.1%, and the prepared sulfonated citric acid chitosan modified polysulfone hemodialysis membrane had excellent anticoagulant performance. However, as the mass fraction of sulfonated citric acid increased from 15% to 22%, the ultrafiltration coefficient of the modified polyethersulfone hemodialysis membrane increased from 54.2mL / m 2 h mmHg decreased to 21.4 mL / m 2·h·mmHg, which causes serious loss of membrane dialysis performance. Post-modification is used to modify the surface of the finished dialysis membrane. In patent CN 110917892A, it is disclosed that the prepared plant polyphenol mixed solution, polyoxazoline mixed solution and anticoagulant modified solution are successively passed into the hemodialysis membrane to obtain a plant polyphenol modified hemodialysis membrane. After 4 hours of simulated dialysis in vitro, 76.7% of urea and 54.1% of lysozyme were removed by the plant polyphenol modified hemodialysis membrane, and the dialysis performance was better than most reported hemodialysis membranes, but the activated partial thromboplastin time in the anticoagulant performance was only 102.1s, and the improvement of the anticoagulant performance was limited. Summary of the invention

[0004] In view of the above defects or improvement needs of the prior art, the present invention provides a core liquid modification method for preparing an anticoagulant hollow fiber membrane and its application, the purpose of which is to prepare a hollow fiber membrane with excellent anticoagulant effect without damaging the dialysis performance, thereby solving the current technical problem that both the anticoagulant effect and the dialysis performance cannot be excellent.

[0005] To achieve the above object, according to one aspect of the present invention, an anticoagulation hollow fiber membrane is provided, comprising a hydrophobic hollow fiber membrane and a modified high molecular polymer formed on the inner surface of the hydrophobic hollow fiber membrane, wherein the modified high molecular polymer is represented by the following formula:

[0006]

[0007] Among them, R1 is a reinforcing carbon chain segment containing a hydrophobic group, R2 is a cross-linked carbon chain segment containing siloxane, and R3 is an anticoagulant carbon chain segment containing a sulfonic acid group or a carboxylic acid group; the number of carbons in the carbon chain segment is 1-200, and x, y, and z are positive integers.

[0008] According to another aspect of the present invention, there is provided a core liquid for preparing an anticoagulation hollow fiber membrane, comprising a modified high molecular polymer, wherein the modified high molecular polymer is represented by the following formula:

[0009]

[0010] Among them, R1 is a reinforcing carbon chain segment containing a hydrophobic group, R2 is a cross-linked carbon chain segment containing siloxane, and R3 is an anticoagulant carbon chain segment containing a sulfonic acid group or a carboxylic acid group; the number of carbons in the carbon chain segment is 1-200, and x, y, and z are positive integers.

[0011] For example, R1 can be a structure shown in the following formula:

[0012]

[0013] Among them, n is 0 to 12.

[0014] For example, R2 can be a structure shown in the following formula:

[0015]

[0016] Exemplarily, R3 may be a structure shown in the following formula:

[0017]

[0018] According to another aspect of the present invention, a method for preparing an anticoagulation hollow fiber membrane by a core liquid modification method is provided, the method comprising the following steps:

[0019] (1) dissolving a reinforcing monomer containing a hydrophobic group, a cross-linking monomer, and an anticoagulant monomer containing a sulfonic acid group or a carboxylic acid group in an organic solvent, stirring the mixture at 180 to 800 r / min on a magnetic stirrer and introducing a protective gas, adding an initiator to cause a polymerization reaction under anhydrous and oxygen-free conditions to obtain a modified high molecular polymer solution, and adding water to the modified high molecular polymer solution to obtain a core liquid;

[0020] (2) The core liquid is added into the flow center tube, and the spinning solution containing the hydrophobic polymer contacts the core liquid after passing through the spinneret, and then passes through a coagulation bath, water washing, and drying to obtain an anticoagulation hollow fiber membrane.

[0021] Preferably, the water content in the core liquid is 20-80 vol%; the mass ratio of the modified high molecular polymer to water in the core liquid is (0.25-4):1.

[0022] Preferably, the mass ratio of the anticoagulant monomer to the reinforcing monomer is 10:(1-100); the mass ratio of the sum of the mass of the anticoagulant monomer and the reinforcing monomer to the mass of the cross-linking monomer is (1-500):5.

[0023] Preferably, the mass ratio of the sum of the mass of the anticoagulant monomer and the reinforcing monomer to the mass of the organic solvent is (1-10):30; the ratio of the mass of the initiator to the sum of the mass of the anticoagulant monomer and the reinforcing monomer is (0.5-5):100.

[0024] Preferably, the hydrophobic group in the reinforcing monomer containing a hydrophobic group includes: phenyl, nitrile, long-chain alkane, perfluoroalkane or ester; wherein the number of carbon atoms in the long-chain alkane is 1-30, and the number of carbon atoms in the perfluoroalkane is 1-30.

[0025] Preferably, the organic solvent is dimethyl sulfoxide, 1,4-dioxane, triethyl phosphate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide; the initiator is at least one of alkyl peroxide, alkyl hydroperoxide, peroxyester, azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyric acid, azobiscyclohexylcarbonitrile, azobisisoheptonitrile, azobisisovaleronitrile, persulfate, and diacyl peroxide.

[0026] Preferably, the polymer matrix in the hydrophobic spinning solution is one of polysulfone, polyethersulfone, polyacrylonitrile, polycarbonate and polyvinylidene fluoride.

[0027] Preferably, the reaction temperature of the polymerization reaction is above 40° C., and the reaction time of the polymerization reaction is 6-48 hours.

[0028] According to another aspect of the present invention, there is provided a use of an anticoagulant hollow fiber membrane for preparing a hemodialyzer.

[0029] In general, compared with the prior art, the above technical solution conceived by the present invention can at least achieve the following beneficial effects.

[0030] (1) The anticoagulant hollow fiber membrane provided by the present invention has an anticoagulant carbon chain segment R3 containing a sulfonic acid group or a carboxylic acid group, a reinforcing carbon chain segment R1 containing a hydrophobic group, and a cross-linked carbon chain segment R2 containing siloxane formed on the modified polymer on the inner surface of the hollow fiber membrane. The modified polymer has three components of reinforcement, cross-linking, and anticoagulation at the same time, and the three components cooperate with each other to achieve the blood compatibility modification of the dialysis membrane. Among them, the reinforcing carbon chain segment R1 and the cross-linked carbon chain segment R2 in the modified polymer can ensure that the anticoagulant unit (i.e., the anticoagulant carbon chain segment R3) of the hollow fiber membrane exists as long as possible and has as many grafts as possible, thereby exerting an anticoagulant effect. The anticoagulant hollow fiber membrane provided by the present invention achieves an excellent anticoagulant effect while maintaining excellent ultrafiltration performance. Not only does it increase the anticoagulant effect (APTT) by 9 times, but the ultrafiltration performance only decreases by ~10%. In the present invention, the modified high molecular polymer is formed only on the inner surface of the hydrophobic hollow membrane, and the anticoagulant effect can be achieved only through the anticoagulant groups of the modified high molecular polymer on the inner surface, which causes little damage to the original pores of the membrane, thereby saving costs and ensuring ultrafiltration performance.

[0031] (2) In the preparation method provided by the present invention, after the casting solution (spinning solution) contacts the core liquid at the outlet of the spinneret, not only does the polymer cool down rapidly to form an initial fiber with a certain mechanical strength, but also, because the spinning solution is a spinning solution containing hydrophobic groups, the modified polymer contains a hydrophobic segment, and the modified polymer is enriched on the inner surface of the fiber through hydrophobic interaction with the fiber surface; thereafter, the modified polymer generates a cross-linked network through cross-linking monomers and entangles with the macromolecules on the fiber surface, and the anticoagulant carbon chain segment is grafted to the inner surface of the dialysis membrane; the anticoagulant carbon chain segment can play an anticoagulant role during hemodialysis. Specifically, when the anticoagulant core liquid contacts the inner wall of the hollow fiber membrane, the reinforcing segment R1 in the modified polymer generates a hydrophobic interaction with the inner wall of the hollow fiber membrane, so that the modified polymer is enriched on the inner surface of the hollow fiber membrane, and then the anticoagulant carbon chain segment R3 is grafted to the inner surface of the fiber under the action of the cross-linking segment R2. The preparation method comprises the following steps: after the monomer, organic solvent and initiator are mixed, water is added after polymerization reaction to obtain core liquid, the core liquid is added to the flow center tube, the spinning liquid is contacted with the core liquid after passing through the spinneret, and a fiber with a certain mechanical strength is formed, and the anticoagulation hollow fiber membrane is obtained after the steps of coagulation bath, water washing, drying, etc. The product can be obtained, the preparation method is simple and quick, and can be widely used in industrial production.

[0032] (3) The hollow fiber membrane provided by the present invention is prepared by using core liquid and spinning liquid. In the prior art, the spinning liquid (casting liquid) is usually modified, which not only causes great damage to the membrane pores and fails to ensure ultrafiltration performance, but also increases the cost. The present invention proposes for the first time to modify the core liquid, which not only has excellent anticoagulant effect, but also ensures ultrafiltration performance.

[0033] (4) In the preparation method provided by the present invention, the method of adding the modified high molecular polymer is a micro-swelling method, and the swelling only occurs on the membrane surface, only partially destroying the membrane surface, with little damage to the original pores of the membrane, so the ultrafiltration performance remains basically unchanged. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 is a schematic diagram of the preparation process of the anticoagulation hollow fiber membrane in Example 1 of the present invention;

[0035] Figure 2 is a scanning electron microscope image of the hollow fiber membrane in Comparative Example 1 of the present invention;

[0036] Figure 3 is a scanning electron microscope image of the hollow fiber membrane in Example 1 of the present invention;

[0037] Figure 4 is the infrared spectra of the hollow fiber membranes in Comparative Example 1 and Example 1 of the present invention;

[0038] Figure 5It is the X-ray photoelectron spectrum of the hollow fiber membrane in Comparative Example 1 and Example 1 of the present invention. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0040] Example 1

[0041] The present invention provides an anticoagulation hollow fiber membrane, see Figure 1 , which is prepared by the following steps:

[0042] (1) Add 7.5 g of sodium p-styrene sulfonate to 120.00 mL of N,N-dimethylacetamide and stir thoroughly until the solution is clear and transparent. Then add 7.5 g of styrene and 6.6 g of vinyl triethoxysilane coupling agent. Adjust the magnetic stirrer speed to 600 r / min, blow nitrogen for 1 h, then add 0.38 g of azobisisobutyronitrile as an initiator and heat to 60°C for 12 h. After the reaction is completed, a polymer modified reaction solution can be obtained.

[0043] (2) Add 120 g of water to the reaction solution to obtain core liquid.

[0044] (3) The core liquid is added to the flow center tube, and the spinning liquid contacts the core liquid after passing through the spinneret to form a fiber with a certain mechanical strength. After a coagulation bath, water washing, drying and other steps, an anticoagulation hollow fiber membrane can be obtained. After encapsulating the hollow fiber membrane, a dialyzer can be obtained.

[0045] The hollow fiber membrane was measured by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, and the inner wall of the hollow fiber membrane was observed by scanning electron microscope. The modified membrane fibers were taken out and tested by coagulation experiment. The results showed that the activated partial thromboplastin time (APTT) and prothrombin time (PT) of the membrane fibers modified by this embodiment were 475 seconds and 40.8 seconds respectively. The ultrafiltration coefficient was 14.8 (mLmmHg -1 h -1 ), urea clearance rate was 161.4mL / min, creatinine clearance rate was 138.1mL / min, lysozyme clearance rate was 58.6mL / min, and after cleaning, the APTT and PT performances could reach 186.2 and 21.5s.

[0046] Example 2

[0047] The embodiment of the present invention provides an anticoagulation hollow fiber membrane, which is prepared by the following steps:

[0048] (1) 11.4 g of sodium p-styrene sulfonate was added to 120.00 mL of N,N-dimethylacetamide, and the mixture was stirred thoroughly until the solution was clear and transparent. Then, 10.2 g of vinyl triethoxysilane coupling agent was added, and the stirring was adjusted to 600 r / min on a magnetic stirrer. Nitrogen was introduced for 1 h, and then 0.38 g of azobisisobutyronitrile was added as an initiator and the temperature was raised to 60° C. The reaction was allowed to react for 12 h. After the reaction was completed, a polymer modified reaction solution was obtained.

[0049] (2) Add 120 g of water to the reaction solution to obtain core liquid.

[0050] (3) The core liquid is added to the flow center tube, and the spinning liquid contacts the core liquid after passing through the spinneret to form a fiber with a certain mechanical strength. After a coagulation bath, water washing, drying and other steps, an anticoagulation hollow fiber membrane can be obtained. After encapsulating the hollow fiber membrane, a dialyzer can be obtained.

[0051] The modified membrane was taken out and subjected to a coagulation test. The results showed that the activated partial thromboplastin time (APTT) and prothrombin time (PT) of the modified membrane were 285 seconds and 28 seconds, respectively. After 4 hours of washing, the APTT and PT were 112.6s and 19.7s, respectively. The ultrafiltration coefficient was 13.8 (mL mmHg -1 h -1 ), urea clearance was 161.5 mL / min, creatinine clearance was 136.5 mL / min, and lysozyme clearance was 55.1 mL / min.

[0052] Example 3

[0053] The embodiment of the present invention provides an anticoagulation hollow fiber membrane, which is prepared by the following steps:

[0054] (1) Add 10.8 g of sodium p-styrene sulfonate to 120.00 mL of N,N-dimethylacetamide, stir thoroughly until the solution is clear and transparent, then add 10.8 g of styrene, stir at 600 r / min on a magnetic stirrer, introduce nitrogen for 1 h, then add 0.38 g of azobisisobutyronitrile as an initiator and heat to 60°C for 12 h. After the reaction is completed, a polymer reaction solution can be obtained.

[0055] (2) Add 120 g of water to the reaction solution to obtain core liquid.

[0056] (3) The core liquid is added to the flow center tube, and the spinning liquid contacts the core liquid after passing through the spinneret to form a fiber with a certain mechanical strength. After a coagulation bath, water washing, drying and other steps, an anticoagulation hollow fiber membrane can be obtained. After encapsulating the hollow fiber membrane, a dialyzer can be obtained.

[0057] The modified membrane was taken out and subjected to a coagulation test. The results showed that the activated partial thromboplastin time (APTT) and prothrombin time (PT) of the modified membrane were 108.5 seconds and 19.5 seconds, respectively. After 4 hours of washing, the APTT and PT were 54.5s and 15.3s, respectively. The ultrafiltration coefficient was 14.2 (mL mmHg -1 h -1 ), urea clearance was 158.4 mL / min, creatinine clearance was 135.4 mL / min, and lysozyme clearance was 57.6 mL / min.

[0058] Example 4

[0059] The embodiment of the present invention provides an anticoagulation hollow fiber membrane, which is prepared by the following steps:

[0060] (1) 11.4 g of styrene and 10.2 g of vinyl triethoxysilane coupling agent were added to 120.00 mL of N,N-dimethylacetamide, and the stirring was adjusted to 600 r / min on a magnetic stirrer. Nitrogen was introduced for 1 hour, and then 0.38 g of azobisisobutyronitrile was added as an initiator and the temperature was raised to 60° C. The reaction was allowed to react for 12 hours. After the reaction was completed, a polymer modified reaction solution was obtained.

[0061] (2) Add 120 g of water to the reaction solution to obtain core liquid.

[0062] (3) The core liquid is added to the flow center tube, and the spinning liquid contacts the core liquid after passing through the spinneret to form a fiber with a certain mechanical strength. After a coagulation bath, water washing, drying and other steps, an anticoagulation hollow fiber membrane can be obtained. After encapsulating the hollow fiber membrane, a dialyzer can be obtained.

[0063] The modified membrane was taken out and then tested for coagulation. The results showed that the activated partial thromboplastin time (APTT) and prothrombin time (PT) of the modified membrane were 52.2 seconds and 14.8 seconds respectively. The ultrafiltration coefficient was 14.2 (mL mmHg -1 h -1 ), urea clearance was 156.8 mL / min, creatinine clearance was 133.6 mL / min, and lysozyme clearance was 56.9 mL / min.

[0064] Example 5

[0065] The embodiment of the present invention provides an anticoagulation hollow fiber membrane, which is prepared by the following steps:

[0066] (1) 7.5 g of sodium vinyl sulfonate was added to 120.00 mL of N,N-dimethylacetamide, and the mixture was stirred thoroughly until the solution was clear and transparent. Then, 7.5 g of styrene and 6.6 g of vinyl triethoxysilane coupling agent were added. The stirring speed was adjusted to 600 r / min on a magnetic stirrer, and nitrogen was introduced for 1 h. Then, 0.38 g of azobisisobutyronitrile was added as an initiator and the temperature was raised to 60° C. The reaction was allowed to react for 12 h. After the reaction was completed, a polymer modified reaction solution was obtained.

[0067] (2) Add 120 g of water to the reaction solution to obtain core liquid.

[0068] (3) The core liquid is added to the flow center tube, and the spinning liquid contacts the core liquid after passing through the spinneret to form a fiber with a certain mechanical strength. After a coagulation bath, water washing, drying and other steps, an anticoagulation hollow fiber membrane can be obtained. After encapsulating the hollow fiber membrane, a dialyzer can be obtained.

[0069] The modified membrane was taken out and then tested for coagulation. The results showed that the activated partial thromboplastin time (APTT) and prothrombin time (PT) of the modified membrane were 292 seconds and 28.9 seconds respectively. The ultrafiltration coefficient was 14.4 (mL mmHg -1 h -1 ), urea clearance was 160.0 mL / min, creatinine clearance was 137.5 mL / min, and lysozyme clearance was 56.5 mL / min.

[0070] Comparative Example 1

[0071] The comparative example of the present invention provides an anticoagulation hollow fiber membrane, which is prepared by the following steps:

[0072] (1) Add 120 g of water to 120.00 mL of N,N-dimethylacetamide to obtain a core solution.

[0073] (2) The core liquid is added to the flow center tube, and the spinning liquid contacts the core liquid after passing through the spinneret to form a fiber with a certain mechanical strength. After a coagulation bath, water washing, drying and other steps, an anticoagulation hollow fiber membrane can be obtained. After encapsulating the hollow fiber membrane, a dialyzer can be obtained.

[0074] The hollow fiber membrane was tested by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, and the inner wall of the hollow fiber membrane was observed by scanning electron microscope. The modified membrane fibers were taken out and subjected to coagulation test. The results showed that the activated partial thromboplastin time (APTT) and prothrombin time (PT) of the membrane fibers modified by this embodiment were 51.2 seconds and 14.6 seconds respectively. The ultrafiltration coefficient was 16 (mLmmHg-1 h -1 ), urea clearance was 165 mL / min, creatinine clearance was 145 mL / min, and lysozyme clearance was 68.4 mL / min.

[0075] Figure 1 is a schematic diagram of the preparation of hollow fiber membranes. Figure 2 and Figure 3 It can be seen from the scanning electron microscope images that the pore size of the hollow fiber membrane did not change significantly before and after modification.

[0076] pass Figure 4 and Figure 5 It can be seen that in the infrared spectrum, 1485 cm -1 、1580cm -1 With 1100cm -1 、1150cm -1 The peaks represented by benzene rings and sulfonic acid groups were enhanced, silicon elements newly appeared in XPS, and the anticoagulant polymer was successfully grafted onto the membrane.

[0077] It can be seen from the above embodiments and comparative examples that:

[0078] 1. In Example 2, a modified high molecular polymer lacking a reinforcing monomer is added, which affects the APTT and PT performances due to the poor compatibility of the high molecular polymer with the membrane.

[0079] 2. In Example 3, a modified high molecular polymer lacking a cross-linking monomer was added. Since the anticoagulant high molecular polymer was not fixed to the membrane, the APTT and PT performances were affected. After 4 hours of washing, the APTT and PT values ​​basically returned to those before modification.

[0080] 3. In Example 4, the modified polymer lacking anticoagulant monomers was added, and the anticoagulant properties represented by APTT and PT were basically not improved. 4. When only three monomers were present, the modified polymer simultaneously exerted its effects through the three units of reinforcement, cross-linking and anticoagulant, and the anticoagulant properties represented by APTT and PT were excellent.

[0081] 5. All examples showed that the ultrafiltration coefficient, creatinine, urea and lysozyme clearance rates decreased within 13%, and the dialysis performance was good.

[0082] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing an anticoagulation hollow fiber membrane by a core liquid modification method, characterized in that: The method comprises the following steps: (1) dissolving styrene monomer, vinyl triethoxysilane crosslinking monomer and sodium p-styrene sulfonate anticoagulant monomer or sodium vinyl sulfonate anticoagulant monomer in an organic solvent, introducing a protective gas, adding an initiator to cause a polymerization reaction under anhydrous and oxygen-free conditions to obtain a modified high molecular polymer solution, and adding water to the modified high molecular polymer solution to obtain a core liquid; the mass ratio of the anticoagulant monomer to the styrene monomer is 10:(1-100); the mass ratio of the sum of the mass of the anticoagulant monomer and the styrene monomer to the mass of the crosslinking monomer is (1-500):5; (2) The core liquid is added into the flow center tube, and the spinning solution containing the hydrophobic polymer contacts the core liquid after passing through the spinneret, and then passes through a coagulation bath, water washing, and drying to obtain an anticoagulation hollow fiber membrane.

2. The method according to claim 1, characterized in that The water content in the core liquid is 20-80 vol%; the mass ratio of the modified high molecular polymer to water in the core liquid is (0.25-4):

1.

3. The method according to claim 1, characterized in that The mass ratio of the sum of the mass of the anticoagulant monomer and the styrene monomer to the mass of the organic solvent is (1-10):30; the ratio of the mass of the initiator to the sum of the mass of the anticoagulant monomer and the styrene monomer is (0.5-5):

100.

4. The method according to claim 1, characterized in that The organic solvent is dimethyl sulfoxide, 1,4-dioxane, triethyl phosphate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide; the initiator is at least one of alkyl peroxide, alkyl hydroperoxide, peroxyester, azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyric acid, azobiscyclohexylcarbonitrile, azobisisoheptonitrile, azobisisovaleronitrile, persulfate, and diacyl peroxide.

5. The method according to claim 1, characterized in that The hydrophobic polymer matrix in the spinning solution is one of polysulfone, polyethersulfone, polyacrylonitrile, polycarbonate and polyvinylidene fluoride.

6. The method according to claim 1, characterized in that The reaction temperature of the polymerization reaction is above 40° C., and the reaction time of the polymerization reaction is 6-48 hours.

7. An anticoagulation hollow fiber membrane, characterized in that: Obtained by the method described in any one of claims 1 to 6.

8. An application of the anticoagulation hollow fiber membrane according to claim 7, characterized in that: Used to prepare hemodialyzers.

Images