A membrane suitable for blood filtration and preparation method thereof

Abstract

The present invention relates to the technical field of polysulfone membranes, and discloses a membrane suitable for blood filtration and a preparation method thereof, wherein the present invention utilizes 4-[(dimethylamino) methyl] phenol to react with chloromethyl polysulfone membrane to generate quaternization, and then quaternary ammonium salt cations and the sodium sulfonate group of sodium sulfonate propyl tea polyphenols undergo electrostatic interaction, and the phenolic hydroxyl groups introduced simultaneously can form hydrogen bonds and the like with the phenolic hydroxyl groups of sodium sulfonate propyl tea polyphenols, so that the sodium sulfonate propyl tea polyphenols can be firmly modified on the surface of the polysulfone membrane, and are not easy to be washed and removed. A large amount of hydrophilic quaternary ammonium salt cations and sulfonate anions, as well as tea polyphenol structures, are introduced on the surface of polyarylether, and the water contact angle, surface hydrophilicity, DPPH free radical scavenging rate and antioxidant properties of the polysulfone membrane are significantly improved. The membrane suitable for blood filtration prepared by the present invention has broad application prospects in aspects such as blood filtration dialysis membranes.

Description

Technical Field

[0001] The invention relates to the technical field of polyethersulfone membranes, in particular to a membrane suitable for blood filtration and a preparation method thereof. Background Art

[0002] Hemofiltration dialysis membrane can replace some of the functions lost in renal failure, play a role in removing metabolic waste, regulating water, electrolytes and acid-base balance, etc. It is widely used in the treatment of renal failure and medical fields. Traditional hemofiltration dialysis membranes mainly include polyethersulfone membranes, polyvinylidene fluoride membranes, cellulose membranes, etc. Among them, polyethersulfone membranes have good chemical stability, excellent mechanical properties, and good anti-biodegradability, and are widely used in hemofiltration dialysis membranes, ultrafiltration membranes, separation membranes, etc.

[0003] Improving the hydrophilicity and antioxidant properties of polyethersulfone membranes can make polyethersulfone have better practical applications in hemodialysis membranes and other aspects. Master's thesis "Preparation and Performance Study of Hydrophilic Antioxidant Modified Polysulfone Hemodialysis Membrane" and "Preparation and Performance Study of Natural Antioxidant Hydrophilic Modified Polysulfone Hemodialysis Membrane" reported that natural antioxidants such as silybin and resveratrol modified polysulfone membranes to improve the hydrophilicity, antioxidant, blood compatibility and other properties of polysulfone hemodialysis membranes. The present invention aims to use biocompatible tea polyphenols to modify the surface of polyethersulfone membranes to improve the hydrophilicity and antioxidant properties of polyethersulfone membranes. Summary of the invention

[0004] The invention solves the problem of poor hydrophilicity and anti-oxidation performance of the polyethersulfone membrane, and expands the practical application of the polyethersulfone membrane in blood filtration dialysis membranes.

[0005] Technical solution: A method for preparing a membrane suitable for blood filtration:

[0006] Step (1), adding chloromethylated polyethersulfone membrane and 4-[(dimethylamino)methyl]phenol to ethanol, stirring to react, taking out the chloromethylated polyethersulfone membrane after the reaction, and washing it with dichloromethane and ethanol in sequence to obtain a cationic modified polyethersulfone membrane.

[0007] Step (2), adding the cationic modified polyethersulfone membrane and sodium sulfonate propyl tea polyphenol into distilled water, stirring for electrostatic adsorption, taking out the cationic modified polyethersulfone membrane after electrostatic adsorption, washing it with water and ethanol in turn, to obtain a membrane suitable for blood filtration.

[0008] Preferably, the mass of 4-[(dimethylamino)methyl]phenol is 30-80% of the mass of the chloromethylated polyethersulfone membrane.

[0009] Preferably, the reaction temperature is 60-70°C and the reaction time is 48-72h.

[0010] Preferably, the mass of sodium sulfonate propyl tea polyphenol is 70-200% of the mass of the cation-modified polyethersulfone membrane.

[0011] Preferably, the temperature during electrostatic adsorption is 40-55° C. and the time is 3-8 hours.

[0012] Preferably, the preparation method of sodium sulfonate propyl tea polyphenol comprises: adding tea polyphenol and 1,3-propane sultone to 1,4-dioxane, dropping sodium hydroxide aqueous solution, after reaction, concentrating under reduced pressure to remove 1,4-dioxane, adding saturated sodium chloride solution and ethyl acetate, extracting by oscillation, standing to separate layers, drying the ethyl acetate phase with anhydrous sodium sulfate, filtering and concentrating under reduced pressure to obtain sodium sulfonate propyl tea polyphenol.

[0013] Preferably, the mass of 1,3-propane sultone is 34-48% of tea polyphenols.

[0014] Preferably, the reaction temperature is 65-80°C and the reaction time is 4-7h.

[0015] Preferably, the preparation method of the chloromethylated polyethersulfone membrane comprises: heating the chloromethylated polyethersulfone, polyethylene glycol, and N,N-dimethylacetamide to 55-70°C, stirring for 6-12 hours, standing to degas, pouring on the surface of a glass plate, using a coating and drying mechanism to form a membrane, and then soaking in distilled water for 48 hours, changing the water every 6 hours, taking out the membrane, and drying it to obtain a chloromethylated polyethersulfone membrane.

[0016] Technical effect: The present invention utilizes 4-[(dimethylamino)methyl]phenol to undergo quaternization reaction with chloromethyl polyethersulfone membrane, introduces quaternary ammonium salt cations and phenolic hydroxyl groups, and then the quaternary ammonium salt cations and the sodium sulfonate groups of sodium sulfonate propyl tea polyphenols undergo electrostatic interaction, while the introduced phenolic hydroxyl groups and the phenolic hydroxyl groups of sodium sulfonate propyl tea polyphenols can form hydrogen bonds and other interactions, so that the sodium sulfonate propyl tea polyphenols can be firmly modified on the surface of the polyethersulfone membrane and are not easy to be washed off.

[0017] A large amount of hydrophilic quaternary ammonium salt cations and sulfonate anions are introduced into the surface of the polyarylether of the invention, thereby significantly improving the surface hydrophilicity and water contact angle of the polyethersulfone membrane.

[0018] The present invention introduces rich tea polyphenol structures on the surface of the polyethersulfone membrane, significantly improving the DPPH free radical scavenging rate and antioxidant performance of the polyethersulfone membrane. The obtained polyethersulfone membrane has broad application prospects in blood filtration dialysis membranes and the like. DETAILED DESCRIPTION

[0019] In order to make the technical solution of the present invention better understood by the technical personnel in the field, and to make the above-mentioned features, purposes and advantages of the present invention more clearly understood, the present invention is further described below in conjunction with the embodiments. The embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0020] Add 12 g of polyethersulfone, 8 g of chloromethyl methyl ether, and 1.6 g of zinc oxide to 300 mL of chloroform, heat to 60°C in a nitrogen atmosphere, react for 5 hours, pour the solution into methanol for precipitation, filter, wash with methanol, and dry to obtain chloromethylated polyethersulfone.

[0021] Example 1

[0022] (1) Add 5 g of tea polyphenols and 2.2 g of 1,3-propane sultone to 100 mL of 1,4-dioxane, dropwise add 10 mL of 0.073 mg / mL sodium hydroxide aqueous solution, heat to 80°C, react for 5 h, concentrate under reduced pressure to remove 1,4-dioxane, add saturated sodium chloride aqueous solution and ethyl acetate, extract by oscillation, stand for stratification, dry the ethyl acetate phase with anhydrous sodium sulfate, filter and concentrate under reduced pressure to obtain sodium sulfonate propyl tea polyphenols.

[0023] (2) 15 g of chloromethylated polyether sulfone, 30 g of polyethylene glycol, and 200 mL of N,N-dimethylacetamide were heated to 55°C, stirred for 12 h, allowed to stand for degassing, poured onto the surface of a glass plate, and made into a film using a coating and drying machine. The film was then immersed in distilled water for 48 h, with the water changed every 6 h. The film was taken out and dried to obtain a chloromethylated polyether sulfone membrane.

[0024] (3) Add 30 g of chloromethylated polyethersulfone membrane and 9 g of 4-[(dimethylamino)methyl]phenol to 600 mL of ethanol, heat to 65°C, stir and react for 72 hours, take out the polyethersulfone membrane, wash it with dichloromethane and ethanol in turn, and obtain a cation-modified polyethersulfone membrane.

[0025] (4) Add 20 g of cationic modified polyethersulfone membrane and 14 g of sodium sulfonate propyl tea polyphenol to 500 mL of distilled water, heat to 55°C, stir for 3 h for electrostatic adsorption, take out the polyethersulfone membrane, wash it with water and ethanol in turn, and obtain a membrane suitable for blood filtration.

[0026] Example 2

[0027] (1) Add 5 g of tea polyphenols and 2.4 g of 1,3-propane sultone to 100 mL of 1,4-dioxane, dropwise add 10 mL of 0.08 mg / mL sodium hydroxide aqueous solution, heat to 65°C, react for 7 h, concentrate under reduced pressure to remove 1,4-dioxane, add saturated sodium chloride solution and ethyl acetate, extract by oscillation, stand for stratification, dry the ethyl acetate phase with anhydrous sodium sulfate, filter and concentrate under reduced pressure to obtain sodium sulfonate propyl tea polyphenols.

[0028] (2) 15 g of chloromethylated polyether sulfone, 40 g of polyethylene glycol, and 200 mL of N,N-dimethylacetamide were heated to 70°C, stirred for 6 h, allowed to stand for degassing, poured onto the surface of a glass plate, and made into a film using a coating and drying machine. The film was then immersed in distilled water for 48 h, with the water changed every 6 h. The film was taken out and dried to obtain a chloromethylated polyether sulfone membrane.

[0029] (3) Add 30 g of chloromethylated polyethersulfone membrane and 9 g of 4-[(dimethylamino)methyl]phenol to 500 mL of ethanol, heat to 60°C, stir and react for 72 hours, take out the polyethersulfone membrane, and wash it with dichloromethane and ethanol in turn to obtain a cation-modified polyethersulfone membrane.

[0030] (4) Add 20 g of cationic modified polyethersulfone membrane and 14 g of sodium sulfonate propyl tea polyphenol to 500 mL of distilled water, heat to 55°C, stir for 5 h of electrostatic adsorption, take out the polyethersulfone membrane, wash it with water and ethanol in turn, and obtain a membrane suitable for blood filtration.

[0031] Example 3

[0032] (1) Add 5 g of tea polyphenols and 1.7 g of 1,3-propane sultone to 80 mL of 1,4-dioxane, dropwise add 10 mL of 0.06 mg / mL sodium hydroxide aqueous solution, heat to 70°C, react for 4 h, concentrate under reduced pressure to remove 1,4-dioxane, add saturated sodium chloride solution and ethyl acetate, extract by oscillation, stand for stratification, dry the ethyl acetate phase with anhydrous sodium sulfate, filter and concentrate under reduced pressure to obtain sodium sulfonate propyl tea polyphenols.

[0033] (2) 15 g of chloromethylated polyether sulfone, 35 g of polyethylene glycol, and 200 mL of N,N-dimethylacetamide were heated to 60°C, stirred for 12 h, allowed to stand for degassing, poured onto the surface of a glass plate, and made into a film using a coating and drying machine. The film was then immersed in distilled water for 48 h, with the water changed every 6 h. The film was taken out and dried to obtain a chloromethylated polyether sulfone membrane.

[0034] (3) Add 30 g of chloromethylated polyethersulfone membrane and 9 g of 4-[(dimethylamino)methyl]phenol to 500 mL of ethanol, heat to 70°C, stir and react for 48 hours, take out the polyethersulfone membrane, and wash it with dichloromethane and ethanol in turn to obtain a cation-modified polyethersulfone membrane.

[0035] (4) Add 20 g of cationic modified polyethersulfone membrane and 14 g of sodium sulfonate propyl tea polyphenol to 400 mL of distilled water, heat to 40°C, stir for 8 h of electrostatic adsorption, take out the polyethersulfone membrane, wash it with water and ethanol in turn, and obtain a membrane suitable for blood filtration.

[0036] Example 4

[0037] (1) Add 30 g of chloromethylated polyethersulfone membrane (prepared in the same manner as in Example 1) and 14 g of 4-[(dimethylamino)methyl]phenol to 600 mL of ethanol, heat to 65°C, stir and react for 72 h, take out the polyethersulfone membrane, wash it with dichloromethane and ethanol in turn, and obtain a cation-modified polyethersulfone membrane.

[0038] (1) Add 20 g of cationic modified polyethersulfone membrane and 22 g of sodium sulfonate propyl tea polyphenol (prepared in the same manner as in Example 1) to 500 mL of distilled water, heat to 55°C, stir for electrostatic adsorption for 3 h, take out the polyethersulfone membrane, wash it with water and ethanol in turn, and obtain a membrane suitable for blood filtration.

[0039] Example 5

[0040] (1) Add 30 g of chloromethylated polyethersulfone membrane (prepared in the same manner as in Example 1) and 19 g of 4-[(dimethylamino)methyl]phenol to 600 mL of ethanol, heat to 65°C, stir and react for 72 h, take out the polyethersulfone membrane, wash it with dichloromethane and ethanol in turn, and obtain a cation-modified polyethersulfone membrane.

[0041] (1) Add 20 g of cationic modified polyethersulfone membrane and 30 g of sodium sulfonate propyl tea polyphenol (prepared in the same manner as in Example 1) to 500 mL of distilled water, heat to 55°C, stir for electrostatic adsorption for 3 h, take out the polyethersulfone membrane, wash it with water and ethanol in turn, and obtain a membrane suitable for blood filtration.

[0042] Example 6

[0043] (1) Add 30 g of chloromethylated polyethersulfone membrane (prepared in the same manner as in Example 1) and 24 g of 4-[(dimethylamino)methyl]phenol to 600 mL of ethanol, heat to 65°C, stir and react for 72 h, take out the polyethersulfone membrane, wash it with dichloromethane and ethanol in turn, and obtain a cation-modified polyethersulfone membrane.

[0044] (1) Add 20 g of cationic modified polyethersulfone membrane and 40 g of sodium sulfonate propyl tea polyphenol (prepared in the same manner as in Example 1) to 500 mL of distilled water, heat to 55°C, stir for electrostatic adsorption for 3 h, take out the polyethersulfone membrane, wash it with water and ethanol in turn, and obtain a membrane suitable for blood filtration.

[0045] Comparative Example 1

[0046] (1) 15 g of polyethersulfone, 30 g of polyethylene glycol, and 200 mL of N,N-dimethylacetamide were heated to 55°C, stirred for 12 h, allowed to stand for degassing, poured onto a glass plate, and made into a film using a coating and drying machine. The film was then immersed in distilled water for 48 h, with the water changed every 6 h. The film was taken out and dried to obtain a polyethersulfone membrane.

[0047] Comparative Example 2 is a chloromethylated polyethersulfone membrane (prepared in the same manner as in Example 1).

[0048] Comparative Example 3 is a cation-modified polyethersulfone membrane (prepared in the same manner as in Example 1).

[0049] Comparative Example 4

[0050] (1) Add 20 g of a cationic modified polyethersulfone membrane (prepared in the same manner as in Example 1) and 14 g of tea polyphenols to 500 mL of distilled water, heat to 55°C, and stir for electrostatic adsorption for 3 h. Take out the polyethersulfone membrane and wash it with water and ethanol in turn to obtain a membrane suitable for blood filtration.

[0051] Comparative Example 5

[0052] (1) Add 20 g of chloromethyl polyethersulfone membrane (prepared in the same manner as in Example 1) and 14 g of sodium sulfonate propyl tea polyphenol to 500 mL of distilled water, heat to 55°C, stir for electrostatic adsorption for 3 h, take out the polyethersulfone membrane, wash it with water and ethanol in turn, and obtain a membrane suitable for blood filtration.

[0053] The surface water contact angle of the polyethersulfone membrane was tested using a contact angle tester, the value was recorded, and the test was performed 3 times to take the average value.

[0054] 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH) was added to ethanol to prepare a solution with a mass concentration of 0.04 g / L, and then a polyethersulfone membrane (specifications: 3 cm × 3 cm × 0.1 cm) was added as the experimental group. The DPPH solution without the polyethersulfone membrane was used as the blank control group. The DPPH solution was placed at room temperature in the dark for 6 hours, and then the solution was removed and the absorbance at 517 nm was tested. The DPPH free radical scavenging rate R was calculated, R = (A0-A) / A0×100%. A0 is the absorbance of the blank control group. A is the absorbance of the experimental group. The test results are shown in Table 1.

[0055] Table 1: Test results

[0056]

[0057] As shown in Table 1, in Example 1-6, 4-[(dimethylamino)methyl]phenol and chloromethyl polyethersulfone membrane are quaternized, quaternary ammonium salt cations and phenolic hydroxyl groups are introduced, and quaternary ammonium salt cations and sodium sulfonate groups of sodium sulfonate propyl tea polyphenols are electrostatically interacted, and the introduced phenolic hydroxyl groups can form hydrogen bonds and other interactions with the phenolic hydroxyl groups of sodium sulfonate propyl tea polyphenols, so that sodium sulfonate propyl tea polyphenols can be firmly modified on the surface of polyethersulfone membrane and are not easy to be washed and removed; hydrophilic quaternary ammonium salt cations and sulfonate anions are introduced on the surface of polyethersulfone membrane, which significantly improves the surface hydrophilicity and water contact angle of polyethersulfone membrane. At the same time, abundant tea polyphenol structures are introduced on the membrane surface, which significantly improves the DPPH free radical scavenging rate and antioxidant performance of polyethersulfone membrane.

[0058] Comparative Example 1 is a polyethersulfone membrane, and Comparative Example 2 is a chloromethylated polyethersulfone membrane. The membrane surface does not contain hydrophilic quaternary ammonium salt cations and sulfonate anions. The surface water contact angle of the polyethersulfone membrane is large and the hydrophilicity is poor. In addition, it does not contain tea polyphenols. The polyethersulfone membrane has almost no DPPH free radical scavenging rate and poor antioxidant performance.

[0059] Compared with Example 1, Comparative Example 3 is a cation-modified polyethersulfone membrane, and the water contact angle is significantly smaller than that of Comparative Example 1, and the hydrophilicity changes, but it does not contain sulfonate hydrophilic groups, resulting in a lower water contact angle than Example 1. In addition, without tea polyphenols, the polyethersulfone membrane has almost no DPPH free radical scavenging rate and poor antioxidant performance.

[0060] The modified polyethersulfone membrane of Comparative Example 4 also contains cationic hydrophilic groups, but tea polyphenols do not contain sodium sulfonate groups, and no sulfonate hydrophilic groups are introduced on the surface of the polyethersulfone membrane, resulting in a lower water contact angle than that of Example 1. In addition, tea polyphenols cannot electrostatically interact with the cationic groups of the modified polyethersulfone membrane, and the bonding strength with the polyethersulfone membrane is low, which makes it difficult to effectively load tea polyphenols on the membrane surface, resulting in a low DPPH free radical scavenging rate of the polyethersulfone membrane and poor antioxidant performance.

[0061] Comparative Example 5: Sodium sulfonate propyl tea polyphenols were used to modify the surface of chloromethyl polyether sulfone membrane. Since the chloromethyl polyether sulfone membrane does not contain quaternary ammonium salt cations and phenolic hydroxyl groups, it is impossible to interact with sodium sulfonate propyl tea polyphenols by electrostatic interaction and hydrogen bonding, and it is impossible to effectively graft sodium sulfonate propyl tea polyphenols on the surface of the polyether sulfone membrane. After washing, sodium sulfonate propyl tea polyphenols will be eluted from the surface of the polyether sulfone membrane, resulting in the polyether sulfone membrane not containing sulfonate hydrophilic groups, a large water contact angle, and poor hydrophilicity. The DPPH radical scavenging rate is only 4.4%, which may be due to the fact that the polyether sulfone membrane is not washed cleanly, and some sodium sulfonate propyl tea polyphenols will remain, which has a weak DPPH radical scavenging rate.

[0062] The above is only a preferred specific implementation manner of the present invention, and the protection scope of the present invention is not limited thereto. Any simple change or equivalent replacement of the technical solution that can be obviously obtained by any technician familiar with the technical field within the technical scope disclosed in the present invention falls within the protection scope of the present invention.

Claims

1. A method for preparing a membrane suitable for blood filtration, characterized in that: The preparation method comprises the following steps: Step (1), adding chloromethylated polyethersulfone membrane and 4-[(dimethylamino)methyl]phenol to ethanol, stirring to react, taking out the chloromethylated polyethersulfone membrane after the reaction, and washing it with dichloromethane and ethanol in sequence to obtain a cationic modified polyethersulfone membrane; Step (2), adding the cationic modified polyethersulfone membrane and sodium sulfonate propyl tea polyphenol into distilled water, stirring for electrostatic adsorption, taking out the cationic modified polyethersulfone membrane after electrostatic adsorption, washing it with water and ethanol in turn, to obtain a membrane suitable for blood filtration.

2. The method for preparing a membrane suitable for blood filtration according to claim 1, characterized in that: The mass of the 4-[(dimethylamino)methyl]phenol is 30-80% of the mass of the chloromethylated polyethersulfone membrane.

3. The method for preparing a membrane suitable for blood filtration according to claim 1, characterized in that: The reaction temperature in step (1) is 60-70°C and the reaction time is 48-72h.

4. The method for preparing a membrane suitable for blood filtration according to claim 1, characterized in that: The mass of the sodium sulfonate propyl tea polyphenol is 70-200% of the mass of the cationic modified polyethersulfone membrane.

5. The method for preparing a membrane suitable for blood filtration according to claim 1, characterized in that: The temperature during the electrostatic adsorption is 40-55° C. and the time is 3-8 hours.

6. The method for preparing a membrane suitable for blood filtration according to claim 1, characterized in that: The preparation method of sodium sulfonate propyl tea polyphenol comprises: adding tea polyphenol and 1,3-propane sultone into 1,4-dioxane, dropping sodium hydroxide aqueous solution, after reaction, concentrating under reduced pressure to remove 1,4-dioxane, adding saturated sodium chloride solution and ethyl acetate, extracting by oscillation, standing and stratifying, drying the ethyl acetate phase with anhydrous sodium sulfate, filtering and concentrating under reduced pressure to obtain sodium sulfonate propyl tea polyphenol.

7. The method for preparing a membrane suitable for blood filtration according to claim 6, characterized in that: The mass of the 1,3-propane sultone is 34-48% of tea polyphenols.

8. The method for preparing a membrane suitable for blood filtration according to claim 6, characterized in that: In the preparation method of sodium sulfonate propyl tea polyphenol, the reaction temperature is 65-80° C. and the reaction time is 4-7 hours.

9. The method for preparing a membrane suitable for blood filtration according to claim 6, wherein the method for preparing the chloromethylated polyethersulfone membrane comprises: Heat chloromethylated polyethersulfone, polyethylene glycol and N,N-dimethylacetamide to 55-70°C, stir for 6-12 hours, let stand to degas, pour on the surface of a glass plate, use a coating and drying mechanism to make a film, then soak in distilled water for 48 hours, change the water every 6 hours, take out the film, and dry it to obtain a chloromethylated polyethersulfone membrane.

10. A membrane suitable for blood filtration obtained by the preparation method according to any one of claims 1 to 9.

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