KR100345505B1 - Hollow fiber membrane and its manufacturing method - Google Patents

Abstract

PURPOSE: Provided is a fabrication method of a polysulfone hollow fiber membrane with improved hydrophilicity and excellent antithrombosis for use in dialysis membrane. CONSTITUTION: In a spinning solution comprising (a) 30 to 80 parts by weight of more than one polar solvent selected from the group consisting of N,N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide and (b) 20 to 40 parts by weight of polysulfone polymer for use in the fabrication of polysulfone hollow fiber membrane, the spinning solution is characterized in that it comprises 1 to 50 parts by weight of hydrophilic vinyl polymer represented by formula I, wherein R1 to R5 is selected from the group consisting of H and shown below as a chemical group (A); at least one among R1 to R5 is selected from the chemical group (A); M is alkali metal; R is alkyl groups having a carbon number of 1 to 5; n is an integer of greater than 1. The spinning solution further comprises 30 to 80 wt.% of more than one congealable solvent selected from the group consisting of water, ethyleneglycol, propylene glycol and polyethyleneglycol.

Description

Hollow fiber membrane and its manufacturing method

[Industrial use]

The present invention relates to a hollow fiber membrane and a method for manufacturing the same, and more particularly, to a polysulfone-like hollow fiber membrane used in an artificial dialysis membrane and a method of manufacturing the same.

[Prior art]

Polysulfones having good mechanical properties and high heat resistance have many applications in each field because of their excellent physical properties, and are particularly used for the production of hollow fiber membranes. However, since the hydrophobicity of the polysulfone material itself is very high, the permeation efficiency is inferior to other materials after the membrane is manufactured, and when applied to an area in contact with blood, such as artificial kidneys, there is a possibility of causing problems such as blood coagulation. Therefore, a method of modifying a polysulfone membrane (membrane) by a suitable method to maintain a high permeability while maintaining the properties of the membrane need to be developed, and also to improve the antithrombogenic properties in the application area in contact with blood Should be.

In order to improve the hydrophilicity and radioactivity of polysulfone, a method of spinning by adding hydrophilic polymers such as polyvinylpyrolidone or polyethyleneglycol (Journal of Applied Polymer Science, Vol. 20, 2377-2394 ) Since the amount of hydrophilic polymer remaining after spinning is not large, the effect is not great. Rather, there is a problem that the remaining hydrophilic polymer may cause water pollution.

The method of immobilizing a hydrophilic polymer using a crosslinking agent is described in Japanese Patent Application Laid-Open No. 58-104940, and the method of crosslinking and fixing a hydrophilic polymer by heat or radiation treatment is disclosed in Japanese Patent Application Laid-Open Nos. Described. However, the above methods are disadvantageous in that the operation is complicated or expensive equipment is required.

In addition, the development of a method for substantially improving the anticoagulation of the polysulfone hollow fiber membrane (hollow fiber membrane) is still insufficient.

[Problems to Solve Invention]

The present invention is to solve the problems of the prior art as described above, an object of the present invention can increase the transmission efficiency for improving the hydrophilicity of the polysulfone membrane (polysulfone membrane), and increase the antithrombogenic properties of the polysulfone membrane It relates to a hollow fiber membrane and a method of manufacturing the same.

[Means for solving the problem]

In order to achieve the object of the present invention as described above, the present invention is 30 to 80 parts by weight of a polar solvent; In the spinning solution for producing a polysulfone hollow fiber membrane containing 20 to 40 parts by weight of the polysulfone polymer dissolved in the polar solvent, 1 to 50 parts by weight of a hydrophilic vinyl polymer represented by the following general formula (I) Provided is a polysulfone hollow fiber membrane comprising a spinning solution for producing a polysulfone hollow fiber membrane and a polysulfone resin as a sea component, and containing a hydrophilic vinyl polymer of general formula (I) as an island component. .

(In the above formula

Selected from the group consisting of at least one of R ₁ ~ R ₅

It is selected from the group consisting of, M is an alkali metal, R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 or more)

In addition, a polymer spinning solution is prepared by dissolving the use of the hollow fiber membrane as an artificial dialysis membrane, the module using the hollow fiber membrane as a separator, the use of the module as an artificial dialysis machine, and a polysulfone polymer and a coagulating solvent in a polar solvent; Spinning the spinning solution into a coagulation bath through a double tubular detention to produce hollow fiber; A method for producing a hollow fiber membrane, comprising the step of washing the hollow fiber with water to dry the membrane, the method comprising: dissolving a hydrophilic vinyl polymer of the general formula (I) in the polar solvent. It provides a method for producing a hollow fiber membrane.

In the present invention described above, it is preferable to use a spinning solution containing the hydrophilic vinyl polymer in an amount of 1 to 20 parts by weight. If the content of the polymer is less than 1 part by weight, there is no hydrophilic effect. If the content of the polymer is more than 20 parts by weight, the stability of the stock solution is poor and the radioactivity is not good.

In the present invention described above, the polar solvent is N, N-dimethylformamide (N, N-dimethylformamide), N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) such as amide (amide) It is preferred that the solvent selected from the group containing a solvent, dimethylsulfoxide (dimethylsulfoxide).

In the present invention, 30 to 80% by weight of a coagulant solvent, which is selected from the group consisting of polyhydric alcohols such as water, ethylene glycol, propyl glycol, and polyethylene glycol, is further included. Include.

In the present invention described above, the polysulfone is preferably used in an amount of 10 to 30 parts by weight, and the solvent is preferably used in an amount of 30 to 80 parts by weight.

[Configuration and Function of Invention]

In the present invention, in order to improve the hydrophilicity of the polysulfone (hereinafter PSF) -based membrane, a polymer as shown in the following formula is added to the polymer spinning solution (dope) composition for preparing the membrane.

(In the season)

Selected from the group consisting of at least one of R ₁ ~ R ₅

It is selected from the group consisting of, M is an alkali metal, R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 or more)

In the above formula

R ₁ , R ₂ , R ₄ and R ₅ are H and R ₃ is When is called polysulfate sodium salt (PSS).

In the present invention, the polysulfone polymer refers to a polymer material composed of the compounds represented by the following formulas (1) and (2).

The use of a polymer such as the above formula has the following advantages compared to the conventional hydrophilic treatment of PSF membranes.

(1) Since the polymer as described above has a large interaction with PSF, the amount of hydrophilic polymer remaining in the membrane after membrane preparation is maximized, and thus the hydrophilization effect is very high. : Polyvinylpyrrolidone (PVP), which is used to enhance the hydrophilic effect of PSF, has excellent hydrophilic effect but little interaction with PSF and only basic force acting between molecules. do. Therefore, the remaining PVP after membrane formation is likely to be easily washed off when the membrane is washed or to fall off and act as a pollution source when the membrane is actually used. For this reason, caution is required in applications where high cleanliness, such as artificial kidneys, should be maintained, and methods for chemically bonding PVP to the PSF backbone are being developed.

In order to solve this drawback, the present invention used poly (sodium 4-styrenesulfonate) (hereinafter referred to as PSS) having good physical bonding strength and good hydrophilic effect. The reason why the physical interaction between PSS and PSF is great is shown in the figure below.

As shown in the preceding figure, there is a phenyl ring in the PSF chain which has abundant electron density by donating electrons on both sides of the phenoxy group and the alkyl group, which are electron donating groups. There is a phenyl ring whose electron density is relatively small due to the electron withdrawing group sulfone group attracting electrons. The attraction between the two phenyl rings with different electron density is called a charge transfer interaction, and this force can be used to induce strong adhesion between the two materials. It was found to be able to escape from the conventional method of inducing chemical bonds with PSF using radiation treatment or special agent, and to find and apply the force that can remain hydrophilic polymer material in PSF membrane by simply strong physical bonding. It will be said that the superiority of the present invention.

(2) improvement of antithrombogenicity of PSF membrane

At present, the antithrombogenicity of membranes is very important in blood-contacting applications such as artificial kidneys, but there is no proper method other than the use with materials that prevent blood clots, such as heparin. However, the excessive use of heparin may cause various side effects in the human body, so its amount should be extremely limited. Therefore, the method of making the surface of the membrane which does not generate a thrombus even if the use of heparin is minimized is known. Among the membranes developed in the present invention, especially the PSS-added membrane has a negative charge because it is a sulfonate, so it has excellent antithrombogenicity Will hold. In addition to the fact that the anti-thrombotic effect of the sulfonate group is not only negatively charged, it also directly interferes with the formation of blood clots. This fact indicates that the molecular structure of heparin, the most commonly used anti-thrombotic agent, is shown in the figure below. It can be understood through the fact that several OH groups in cellulose are substituted with -SOOH groups.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples and comparisons are only preferred embodiments of the present invention to aid in understanding the present invention, and the present invention is not limited to the following examples.

Example 1

17 wt% of polysulfone (p-3500: AMOCO Co., Ltd.), 9 wt% of PSS, and 10 wt% of PEG were stirred and dissolved in 64 wt% of DMF to prepare a transparent spinning stock solution. This spinning stock solution was discharged at a rate of 2.0 g / min from an annular slit mold having an outer diameter of 0.35 mm, an inner diameter of 0.2 mm, and an injection hole diameter of 0.15 mm, and at the same time, water as an internal coagulating solution was injected from the injection hole at a rate of 1.3 g / min. . After 10 cm through the air gap, the hollow fiber was guided to a coagulation bath (water) at 25 ℃ washed by coagulation and wound in a failure shape at a winding speed of 33 m / min. The obtained UFR of the hollow fiber was 250 ml / min / mmHg / m ² and the antithrombogenic property was good.

Examples 2-5

In the same manner as in Example 1 above, only PSS addition amount was changed as shown in Table 1 below to prepare a hollow fiber.

Comparative Examples 1 to 3

Same as Example 1 above, using hollow fiber PVS instead of PSS, or without adding a polymer was prepared hollow fiber.

Permeability (UFR) and antithrombotic properties of each of the hollow fiber membranes obtained in Examples 2 to 5 and Comparative Examples 1 to 3 were measured as follows, and the results are shown in Table 1 below.

(1) Transmission Performance Evaluation (UFR)

A small glass tube module was prepared using 20 strands of hollow fiber of 15 cm in length to calculate the water permeability while maintaining the intermembrane pressure at about 100 mmHg. (UFR: ml / min / mmHg / m ² )

(2) antithrombotic evaluation

The hollow fiber was contacted with blood for 1 hour, and then treated with an aqueous salt solution containing 2.0 wt% glutaraldehyde to fix the adhesive component. Observed. At this time, the number of platelets adhered in 100 nm ² is good when less than 10, usually 10 to 100, it was marked as bad when more than 100.

The hollow fiber membrane prepared according to the present invention showed better UFR and antithrombogenicity than the conventional hollow fiber membrane.

Claims (5)

30 to 80 parts by weight of a polar solvent; In the spinning solution for producing a polysulfone hollow fiber membrane containing 20 to 40 parts by weight of a polysulfone polymer, 1 to 50 parts by weight of a hydrophilic vinyl polymer represented by the following general formula (I); Spinning solution for producing a polysulfone hollow fiber membrane, comprising: (In the above formula R ₁ to R ₅ is H, , , , , Selected from the group consisting of at least one of R ₁ ~ R ₅ , , , , It is selected from the group consisting of, M is an alkali metal, R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 or more) The spinning solution of claim 1, wherein the vinyl polymer is included in an amount of 1 to 20 parts by weight. The spinning solution of claim 1, wherein the polar solvent is selected from the group consisting of N, N-dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. The spinning solution according to claim 1, wherein the spinning solution further comprises 30 to 80% by weight of a coagulant solvent selected from the group consisting of water, ethylene glycol, propylene glycol, and polyethylene glycol. The spinning solution of claim 1, wherein the polysulfone is contained in an amount of 10 to 30 parts by weight, and the solvent is contained in an amount of 30 to 80 parts by weight.