Membrane material with high oxygen permeability and preparation method thereof

Abstract

The invention discloses a high-oxygen-permeability membrane material and a preparation method thereof, and belongs to the technical field of membrane materials. The membrane material is prepared by taking polydimethylsiloxane and polycaprolactone as organic raw materials, adding an inorganic material nano titanium dioxide or graphene, and carrying out solution preparation, cross-linking reaction, casting membrane formation, hot press molding, plasma treatment and surface modification. The polydimethylsiloxane guarantees the oxygen permeability, the polycaprolactone improves the flexibility and the biocompatibility, and the nano inorganic particles enhance the mechanical strength and the antibacterial property. The prepared membrane material is improved in oxygen permeability coefficient, greatly improved in tensile strength and elongation at break, good in hydrophilicity and biocompatibility, low in cytotoxicity and small in hemolysis rate, can be widely applied to medical products such as artificial lungs, wound dressings and contact lenses, and effectively meets the requirements of the medical field for the membrane material with high oxygen permeability and good comprehensive performance.

Description

Technical Field

[0001] The present invention relates to the technical field of membrane material preparation, and more particularly to a high oxygen permeability membrane material and a preparation method thereof. Background Art

[0002] With the development of modern technology, higher performance requirements are being placed on membrane materials. In the medical field, membrane materials are used in products such as artificial lungs, wound dressings, and contact lenses. Artificial lungs require membrane materials that can efficiently exchange oxygen and carbon dioxide to maintain patients' vital signs; wound dressings require appropriate oxygen permeability to promote wound healing; and the oxygen permeability of contact lenses directly affects the wearer's eye health. The oxygen permeability and biocompatibility of membrane materials are directly related to patients' life, health, and user experience.

[0003] Although traditional membrane materials such as pure PDMS membranes have a certain oxygen permeability, they have exposed many defects in actual applications. Their mechanical strength is poor and they are very prone to tensile fracture when subjected to large external forces. They are not suitable for application scenarios that require high material strength. In terms of biocompatibility, pure PDMS membranes may cause cytotoxic reactions, hemolysis, and even lead to thrombosis in medical applications, which greatly limits their clinical application scope. In addition, this type of membrane material has poor anti-pollution performance and is prone to adsorbing substances such as proteins, resulting in a decrease in membrane performance, shortened service life, and increased use costs.

[0004] Therefore, how to provide a preparation method that can significantly improve the oxygen permeability, mechanical strength, biocompatibility and anti-pollution properties of membrane materials has become a key issue that needs to be urgently addressed in the field of membrane materials. Summary of the Invention

[0005] In view of this, the present invention provides an innovative high oxygen permeability membrane material and its preparation method, which improves the material selection and preparation process, effectively overcoming the shortcomings of traditional membrane materials in oxygen permeability, mechanical strength, biocompatibility and anti-pollution, and providing high-performance membrane material solutions for applications in multiple fields.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] First, the present invention provides a method for preparing a high oxygen permeability membrane material, comprising the following steps:

[0008] (1) Add the substrate to a solvent and heat to 60-80°C to dissolve it, preparing a substrate solution with a concentration of 10%-30%, then add inorganic additives and plasticizers, and continue stirring at a stirring speed of 500-1000 r / min for 2-4 hours;

[0009] (2) adding a crosslinking agent to the uniformly dispersed system of step (1), and continuing stirring at 50-70° C. for 1-2 hours to initiate a crosslinking reaction;

[0010] (3) pouring the cross-linked dispersion system of step (2) into a mold, placing it in a vacuum environment for 1-2 hours to remove bubbles, and then standing at room temperature for 24-48 hours to form an initial film;

[0011] (4) placing the primary film obtained in step (3) in a hot press at a temperature of 80-100° C. and a pressure of 5-10 MPa for 10-20 minutes; the hot pressing treatment can further improve the density and mechanical properties of the film material;

[0012] (5) placing the film treated in step (4) in a plasma treatment device and introducing a mixed gas of oxygen and argon for 3-5 minutes;

[0013] (6) Soaking the membrane treated in step (5) in a dispersion containing bioactive molecules at a temperature of 40-60° C. for 1-2 hours, removing the membrane and drying it naturally to obtain a high oxygen permeability membrane material.

[0014] Preferably, the substrate in step (1) is polydimethylsiloxane and polycaprolactone, and the mass ratio of the two is (50-70): (20-30). PDMS has good air permeability and chemical stability and is a key raw material for improving the oxygen permeability of membrane materials. PCL can improve the flexibility and biocompatibility of membrane materials.

[0015] Preferably, the solvent in step (1) is one or more of toluene, tetrahydrofuran, dimethylformamide, and chloroform.

[0016] Preferably, the inorganic additive in step (1) is one or more of nano-titanium dioxide or graphene, and the mass ratio of the inorganic additive to polydimethylsiloxane is (5-10): (50-70). The addition of nano-TiO2 or graphene can enhance the mechanical strength and antibacterial properties of the membrane material. Through a specific ratio of organic-inorganic composite, the oxygen permeability and mechanical strength of the membrane material can be effectively balanced.

[0017] Preferably, the plasticizer in step (1) is dioctyl phthalate, and the mass ratio of the plasticizer to polydimethylsiloxane is (3-5): (50-70). Adding a certain proportion of plasticizer can adjust the flexibility and processing properties of the film material.

[0018] Preferably, the crosslinking agent in step (2) is hydrogenated silicone oil and chloroplatinic acid, the amount of hydrogenated silicone oil added is 1-3% of the mass of polydimethylsiloxane, and the amount of chloroplatinic acid added is 0.05-0.1% of the mass of polydimethylsiloxane. The crosslinking agent system composed of hydrogenated silicone oil and chloroplatinic acid can cause PDMS molecules to undergo crosslinking reaction to form a stable three-dimensional network structure.

[0019] Preferably, the vacuum degree in step (3) is -0.08 to -0.1 MPa.

[0020] Preferably, the volume ratio of oxygen to argon in step (5) is 1:(3-5), and the power of the plasma treatment equipment is 50-100 W. Plasma surface treatment can introduce a large number of active groups (such as hydroxyl groups, carboxyl groups, etc.) on the surface of the membrane material, thereby improving the hydrophilicity and biocompatibility of the membrane material.

[0021] Preferably, the bioactive molecules in step (6) are one or more of collagen or chitosan, the dispersion matrix is water, and the bioactive molecule mass concentration is 10-20%. The bioactive molecules are grafted onto the surface of the membrane material to further improve the biocompatibility and functionality of the membrane material.

[0022] In addition, the present invention also provides a high oxygen permeability membrane material prepared by the method described in the above technical solution.

[0023] It can be seen from the above technical solutions that, compared with the prior art, the present invention discloses a high oxygen permeability membrane material and a preparation method thereof, which has the following beneficial effects:

[0024] The high oxygen permeability membrane material of the present invention has excellent oxygen permeability through the reasonable ratio of polydimethylsiloxane and polycaprolactone organic raw materials, the addition of inorganic raw material particles, and the combination of specific cross-linking and molding processes. The oxygen permeability is increased by 20-50% compared with traditional materials (such as pure PDMS membranes), which can meet the demand for high oxygen permeability in the medical field. The addition of inorganic particles and the application of processes such as hot pressing and molding significantly improve the mechanical strength of the membrane material, greatly improve the tensile strength and elongation at break, and make it less likely to break during use. The surface modification treatment through plasma treatment and grafting modification greatly improves the hydrophilicity and biocompatibility of the membrane material, reduces the irritation and rejection reaction of the material to human tissue, and improves the safety and effectiveness of medical products. DETAILED DESCRIPTION

[0025] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0026] Example 1

[0027] Raw material ratio (parts by mass):

[0028] 60 parts of polydimethylsiloxane, 25 parts of polycaprolactone, 8 parts of nano-titanium dioxide, 4 parts of plasticizer dioctyl phthalate, the amount of hydrogen silicone oil added in the cross-linking agent is 2% of the mass of polydimethylsiloxane, and the amount of chloroplatinic acid is 0.08% of the mass of polydimethylsiloxane.

[0029] The preparation process is:

[0030] (1) Dimethylsiloxane and polycaprolactone were added to toluene and heated to 60-80°C to dissolve to prepare a substrate solution with a concentration of 10%-30%. Nano-titanium dioxide and dioctyl phthalate were then added and stirred at a stirring speed of 8000 r / min for 3 hours.

[0031] (2) Add crosslinking agent and stir at 60°C for 1.5 hours;

[0032] (3) Pour the solution into the mold, place it under a vacuum of -0.09 MPa for 1.5 h to remove bubbles, and then let it stand at room temperature for 36 h to remove the solvent;

[0033] (4) hot pressing at 90°C and 8 MPa for 15 min;

[0034] (5) Place in a plasma treatment device, introduce a mixed gas of oxygen and argon with a volume ratio of 1:4, and treat at a power of 80W for 4 minutes;

[0035] (6) The membrane material was immersed in a collagen dispersion with a mass fraction of 20%, grafted at 50°C for 1.5 hours, and then naturally dried to obtain a finished membrane.

[0036] Example 2

[0037] Raw material ratio (parts by mass):

[0038] 55 parts of polydimethylsiloxane, 28 parts of polycaprolactone, 7 parts of nano-titanium dioxide, 3.5 parts of plasticizer dioctyl phthalate, the amount of hydrogen silicone oil added to the crosslinking agent is 1.8% of the mass of polydimethylsiloxane, and the amount of chloroplatinic acid used is 0.06% of the mass of polydimethylsiloxane.

[0039] The preparation process is:

[0040] (1) Dimethylsiloxane and polycaprolactone were added to toluene and heated to 60-80°C to dissolve to prepare a substrate solution with a concentration of 10%-30%. Nano-titanium dioxide and dioctyl phthalate were then added and stirred at a stirring speed of 8000 r / min for 3 hours.

[0041] (2) Add crosslinking agent and stir at 65°C for 3.5 hours;

[0042] (3) Pour the solution into the mold, place it under a vacuum of -0.08 MPa for 1.2 hours to remove bubbles, and then let it stand at room temperature for 40 hours to remove the solvent;

[0043] (4) hot pressing at 85°C and 7 MPa for 12 min;

[0044] (5) Place in a plasma treatment device, introduce a mixed gas of oxygen and argon with a volume ratio of 1:3.5, and treat at a power of 70 W for 4 minutes;

[0045] (6) The membrane material was immersed in a chitosan dispersion with a mass fraction of 15%, grafted at 45°C for 1.2 hours, and then naturally dried to obtain the finished membrane.

[0046] Example 3

[0047] Raw material ratio (parts by mass):

[0048] 65 parts of polydimethylsiloxane, 22 parts of polycaprolactone, 9 parts of graphene, 4.5 parts of plasticizer dioctyl phthalate, the amount of hydrogenated silicone oil added to the crosslinking agent is 1.5% of the mass of polydimethylsiloxane, and the amount of chloroplatinic acid is 0.05% of the mass of polydimethylsiloxane.

[0049] The preparation process is:

[0050] (1) Dimethylsiloxane and polycaprolactone were added to toluene and heated to 60-80°C to dissolve to prepare a substrate solution with a concentration of 10%-30%. Nano-titanium dioxide and dioctyl phthalate were then added and stirred at a stirring speed of 8000 r / min for 3 hours.

[0051] (2) Add crosslinking agent and stir at 65°C for 1.8 hours;

[0052] (3) Pour the solution into the mold, place it under a vacuum of -0.08 MPa for 1.8 hours to remove bubbles, and then let it stand at room temperature for 30 hours to remove the solvent;

[0053] (4) hot pressing at 95°C and 9 MPa for 18 min;

[0054] (5) Place in a plasma treatment device, introduce a mixed gas of oxygen and argon with a volume ratio of 1:4.5, and treat at 90W power for 4 minutes;

[0055] (6) The membrane material was immersed in a chitosan dispersion with a mass fraction of 15%, grafted at 55°C for 1.5 hours, and then naturally dried to obtain the finished membrane.

[0056] Experimental example

[0057] The membrane materials prepared in Examples 1-3 of the present invention were tested with reference to relevant standards, with pure PDMS membrane used as a comparison. The results are shown in the following table:

[0058]

[0059]

[0060] The above test results show that the membrane material prepared by the present invention has greatly improved oxygen permeability and mechanical strength compared with traditional pure PDMS membrane, and has better biocompatibility.

[0061] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same and similar parts between the various embodiments can be referred to each other. The above description of the disclosed embodiments enables professionals and technicians in this field to implement or use the present invention. Various modifications to these embodiments will be apparent to professionals and technicians in this field, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a high oxygen permeability membrane material, characterized in that: The following steps are involved: (1) Add the substrate to a solvent and heat to 60-80°C to dissolve it, preparing a substrate solution with a concentration of 10%-30%, then add inorganic additives and plasticizers, and continue stirring at a stirring speed of 500-1000 r / min for 2-4 hours; (2) adding a crosslinking agent to the uniformly dispersed system of step (1), and continuing stirring at 50-70° C. for 1-2 hours to initiate a crosslinking reaction; (3) pouring the cross-linked dispersion system of step (2) into a mold, placing it in a vacuum environment for 1-2 hours to remove bubbles, and then standing at room temperature for 24-48 hours to form an initial film; (4) placing the primary film obtained in step (3) in a hot press at a temperature of 80-100° C. and a pressure of 5-10 MPa for 10-20 min; (5) placing the film treated in step (4) in a plasma treatment device and introducing a mixed gas of oxygen and argon for 3-5 minutes; (6) Soaking the membrane treated in step (5) in a dispersion containing bioactive molecules at a temperature of 40-60° C. for 1-2 hours, removing the membrane and drying it naturally to obtain a high oxygen permeability membrane material.

2. The method for preparing a high oxygen permeability membrane material according to claim 1, characterized in that: The substrate in step (1) is polydimethylsiloxane and polycaprolactone, and the mass ratio of the two is (50-70): (20-30).

3. The method for preparing a high oxygen permeability membrane material according to claim 1, characterized in that: The solvent in step (1) is one or more of toluene, tetrahydrofuran, dimethylformamide and chloroform.

4. The method for preparing a high oxygen permeability membrane material according to claim 1, characterized in that: The inorganic additive in step (1) is one or more of nano-titanium dioxide or graphene, and the mass ratio of the inorganic additive to polydimethylsiloxane is (5-10): (50-70).

5. The method for preparing a high oxygen permeability membrane material according to claim 1, characterized in that: The plasticizer in step (1) is dioctyl phthalate, and the mass ratio of the plasticizer to polydimethylsiloxane is (3-5): (50-70).

6. The method for preparing a high oxygen permeability membrane material according to claim 1, characterized in that: The crosslinking agents in step (2) are hydrogenated silicone oil and chloroplatinic acid, the amount of hydrogenated silicone oil added is 1-3% of the mass of polydimethylsiloxane, and the amount of chloroplatinic acid added is 0.05-0.1% of the mass of polydimethylsiloxane.

7. The method for preparing a high oxygen permeability membrane material according to claim 1, characterized in that: The vacuum degree in step (3) is -0.08 to -0.1 MPa.

8. The method for preparing a high oxygen permeability membrane material according to claim 1, characterized in that: The volume ratio of oxygen to argon in step (5) is 1:(3-5), and the power of the plasma treatment equipment is 50-100W.

9. The method for preparing a high oxygen permeability membrane material according to claim 1, characterized in that: In step (6), the bioactive molecules are one or more of collagen or chitosan, the dispersion matrix is water, and the mass concentration of the bioactive molecules is 10-20%.

10. A high oxygen permeability membrane material prepared by the method according to any one of claims 1 to 9.

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