Amino acid derivative polymeric membrane material and preparation method thereof

Abstract

The invention relates to the field of membrane material preparation, in particular to an amino acid derivative polymer membrane material and a preparation method thereof. The preparation method provided by the invention comprises the following steps: S1, preparing a polymer solution; S2, forming and depositing a membrane; S3, carrying out surface modification on the membrane; and S4, carrying out crosslinking treatment. The functional polymer membrane material is synthesized through the amino acid derivative, selective separation of specific ions or molecules can be achieved, and good biocompatibility, stability and application prospects are achieved. The technology can be widely applied to multiple fields of biological separation, environment purification, drug delivery and the like, and has remarkable innovativeness and practical value.

Description

Technical Field

[0001] The invention relates to the field of membrane material preparation, and in particular to an amino acid derivative polymer membrane material and a preparation method thereof. Background Art

[0002] As an advanced separation medium, polymer membrane materials have shown great application potential in many scientific and industrial fields, especially in key areas such as biological separation, environmental protection, drug delivery and seawater desalination. These membrane materials can effectively screen and separate substances with their unique structural and functional characteristics, providing strong technical support for the development of related industries.

[0003] In the field of bioseparation, polymer membranes can efficiently separate and purify biomacromolecules such as proteins and nucleic acids based on their molecular size, charge properties or bioaffinity, which is crucial for the development and production of biopharmaceutical products. However, existing polymer membrane materials still have significant deficiencies in selectivity. Especially when processing complex biological samples, due to the diverse components and complex interactions in the samples, membrane materials often find it difficult to achieve high-precision separation of target substances, which limits their application in high-precision bioseparation.

[0004] In terms of environmental protection, polymer membranes play an important role in wastewater treatment, gas separation and other fields. However, the problem of poor selectivity also makes it difficult for membrane materials to achieve ideal purification effects when treating wastewater containing multiple pollutants. In addition, insufficient biocompatibility is also a major challenge facing current polymer membrane materials. In biomedical applications, membrane materials need to be in direct contact with organisms. If the biocompatibility is poor, it may induce immune responses or cytotoxicity and cause damage to the organism, which seriously limits the widespread application of membrane materials in the biomedical field.

[0005] In summary, in view of the problems existing in the selectivity, biocompatibility and stability of existing polymer membrane materials, developing a functionalized polymer membrane material with high selectivity, good biocompatibility and strong stability has become a key issue to be solved in the current scientific and technological field. This is not only of great significance for promoting technological progress in the fields of biological separation, environmental protection, drug delivery and seawater desalination, but also will provide strong technical support for the sustainable development of related industries. Summary of the invention

[0006] In view of the above existing technical problems, the present invention aims to provide an amino acid derivative polymer membrane material and a preparation method thereof. This preparation method synthesizes a functionalized polymer membrane material through amino acid derivatives, which can achieve selective separation of specific ions or molecules, and has good biocompatibility, stability and application prospects. This technology can be widely applied in many fields such as biological separation and environmental purification, and has significant innovation and practical value.

[0007] The present invention discloses a preparation method of an amino acid derivative polymer membrane material, including the following preparation steps:

[0008] S1 Polymer solution preparation: Add the amino acid derivative to a reaction flask, add a solvent to dissolve it, then add polyether and stir to mix and dissolve. After complete dissolution, add an initiator, control the reaction temperature and reaction time for polymerization reaction, and cool after the reaction ends to obtain a polymer solution;

[0009] S2 Membrane forming and deposition: Uniformly coat the polymer solution obtained in step S1 on a smooth plate, and use the spin coating method to form the membrane. After coating, perform heat treatment, control the temperature and time of heat treatment, and obtain a membrane;

[0010] S3 Surface modification of the membrane: Immerse the membrane obtained in step S2 in a mercaptoacetic acid solution, then heat and react. After the reaction ends, wash with deionized water and then immerse in a chloroethylamine solution for heating and reaction. After the reaction ends, take out the membrane, wash it with deionized water until clean, and place it in a dryer for drying to obtain a surface-modified membrane;

[0011] S4 Crosslinking treatment: Place the surface-modified membrane obtained in step S3 in a glassware, then add a pentanediol solution and heat up to carry out a crosslinking reaction. After crosslinking is completed, wash and dry to obtain an amino acid derivative polymer membrane material.

[0012] Preferably, in the S1 polymer solution preparation step, the solvent is dimethyl sulfoxide.

[0013] Preferably, in the S1 polymer solution preparation step, the mass concentration of the amino acid derivative is 0.1 - 0.5 g / L.

[0014] Preferably, in the S1 polymer solution preparation step, the mass ratio of the amino acid derivative to the polyether is 1:(1 - 1.5).

[0015] Preferably, in the S1 polymer solution preparation step, the temperature of the polymerization reaction is 80 - 120 °C, and the reaction time is 2 - 4 h.

[0016] Preferably, in the S2 membrane forming and deposition step, the temperature of the heat treatment is 110 - 130 °C, and the time is 0.5 - 3 h.

[0017] Preferably, in the forming and depositing step of the S2 film, the thickness of the film is 10 - 50 μm.

[0018] Preferably, in the surface modification step of the S3 film, the mass fraction of the mercaptoacetic acid solution is 2 - 6%; the mass fraction of the chloroethylamine solution is 1 - 3%; the drying temperature of the dryer is 60 - 70 °C.

[0019] Preferably, in the S4 crosslinking treatment, the mass fraction of the pentanediol solution is 10 - 20%; the temperature of the crosslinking reaction is 50 - 70 °C, and the time of the crosslinking reaction is 3 - 6 h.

[0020] An amino acid derivative polymer membrane material, an amino acid derivative polymer membrane material prepared by any of the above - mentioned preparation methods of amino acid derivative polymer membrane materials.

[0021] Compared with the prior art, the beneficial effects of the present invention are:

[0022] In the preparation method of an amino acid derivative polymer membrane material provided by the present invention, first, an amino acid derivative and a polyether are polymerized to form a polymer to endow the membrane material with better biocompatibility; then the heat - treated membrane has good mechanical strength and stability; the heat - treated membrane is surface - modified to introduce thiol groups to adjust the hydrophobicity of the membrane and introduce amino groups to adjust the charge state of the membrane surface, thereby enhancing the separation ability of the membrane; the surface - modified membrane reacts with a crosslinking agent to form a three - dimensional network structure, further improving the mechanical strength and stability of the membrane material.

[0023] The amino acid derivative polymer membrane material prepared by the above - mentioned preparation method has better biocompatibility compared with traditional membrane materials. By adjusting the hydrophilicity / hydrophobicity, charge property, etc. of the membrane, selective separation of different ions or molecules can be achieved, enhancing the application range of the membrane; it combines high selectivity and multifunctionality, making the membrane material not only suitable for biological separation, but also widely applicable to fields such as environmental purification, drug delivery, and sensors, and has high market application value. Specific Embodiments

[0024] The following embodiments are provided to better further understand the present invention, which is not limited to the best embodiment, and does not constitute a limitation to the content and protection scope of the present invention. Any product obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior art features and being the same or similar to the present invention falls within the protection scope of the present invention.

[0025] For those not specifying specific experimental procedures or conditions in the examples, the operations or conditions of the conventional experimental procedures described in the literature in this field can be followed. For reagents or instruments without indicating the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0026] Example 1: A preparation method of an amino acid derivative polymer membrane material, comprising the following steps:

[0027] S1 Polymer solution preparation: Add the amino acid derivative to a reaction flask, add dimethyl sulfoxide for dissolution, and the mass concentration of the amino acid derivative after dissolution is 0.1 g / L; then add polyether and stir to mix and dissolve, where the mass ratio of the amino acid derivative to polyether is 1:1; after complete dissolution, add the initiator sodium persulfate, control the reaction temperature at 80 °C, and carry out a polymerization reaction for 2 h. After the reaction is completed, cool to room temperature to obtain a polymer solution.

[0028] S2 Membrane forming and deposition: Uniformly coat the polymer solution obtained in step S1 on a smooth plate, and use the spin coating method for membrane forming. After coating, perform heat treatment, control the heat treatment temperature at 110 °C, and the heat treatment time is 3 h to obtain a membrane with a thickness of 50 μm.

[0029] S3 Surface modification of the membrane: Immerse the membrane obtained in step S2 in a 2% thioglycolic acid solution, then heat to 40 °C and react for 3 h. After the reaction is completed, wash with deionized water and then immerse in a 1% chloroethylamine solution and heat to 80 °C and react for 2 h. After the reaction is completed, take out the membrane, wash it with deionized water until clean, and place it in a dryer with the dryer temperature set at 60 °C for drying to obtain a surface-modified membrane.

[0030] S4 Crosslinking treatment: Place the surface-modified membrane obtained in step S3 in a glassware, then add a 10% pentanediol solution and heat to 70 °C for crosslinking reaction. After 5 h of crosslinking reaction, wash and dry to obtain the amino acid derivative polymer membrane material.

[0031] Example 2: A preparation method of an amino acid derivative polymer membrane material, comprising the following steps:

[0032] S1 Polymer solution preparation: Add the amino acid derivative to a reaction flask, add dimethyl sulfoxide for dissolution, and the mass concentration of the amino acid derivative after dissolution is 0.1 g / L; then add polyether and stir to mix and dissolve, where the mass ratio of the amino acid derivative to polyether is 1:1; after complete dissolution, add the initiator sodium persulfate, control the reaction temperature at 100 °C, and carry out a polymerization reaction for 3 h. After the reaction is completed, cool to room temperature to obtain a polymer solution.

[0033] Formation and deposition of the S2 film: The polymer solution obtained in step S1 is evenly coated on a smooth plate, and film formation is carried out by spin coating. After coating, heat treatment is carried out, controlling the heat treatment temperature at 120 °C and the heat treatment time at 1.5 h to obtain a film with a thickness of 30 μm.

[0034] Surface modification of the S3 film: The film obtained in step S2 is immersed in a mercaptoacetic acid solution with a mass fraction of 2%, and then heated to 50 °C for reaction for 2.5 h. After the reaction is completed, it is washed with deionized water and then immersed in a chloroethylamine solution with a mass fraction of 1% and heated to 90 °C for reaction for 1.5 h. After the reaction is completed, the film is taken out, washed with deionized water, and then placed in a dryer with the dryer temperature set at 65 °C for drying to obtain a surface-modified film.

[0035] S4 Crosslinking treatment: The surface-modified film obtained in step S3 is placed in a glassware, and then a pentanediol solution with a mass fraction of 15% is added and heated to 60 °C for crosslinking reaction. After 6 h of crosslinking reaction, it is washed and dried to obtain an amino acid derivative polymer film material.

[0036] Example 3: A method for preparing an amino acid derivative polymer film material, comprising the following steps:

[0037] S1 Polymer solution preparation: Add an amino acid derivative to a reaction flask, add dimethyl sulfoxide for dissolution, and the mass concentration of the amino acid derivative after dissolution is 0.1 g / L; then add polyether and stir and mix for dissolution, where the mass ratio of the amino acid derivative to polyether is 1:1; after all are dissolved, add initiator sodium persulfate, control the reaction temperature at 120 °C, and the reaction time at 3 h for polymerization reaction. After the reaction is completed, cool to room temperature to obtain a polymer solution.

[0038] Formation and deposition of the S2 film: The polymer solution obtained in step S1 is evenly coated on a smooth plate, and film formation is carried out by spin coating. After coating, heat treatment is carried out, controlling the heat treatment temperature at 130 °C and the heat treatment time at 0.5 h to obtain a film with a thickness of 10 μm.

[0039] Surface modification of the S3 film: The film obtained in step S2 is immersed in a mercaptoacetic acid solution with a mass fraction of 2%, and then heated to 60 °C for reaction for 2 h. After the reaction is completed, it is washed with deionized water and then immersed in a chloroethylamine solution with a mass fraction of 1% and heated to 100 °C for reaction for 1 h. After the reaction is completed, the film is taken out, washed with deionized water, and then placed in a dryer with the dryer temperature set at 70 °C for drying to obtain a surface-modified film.

[0040] S4 Crosslinking treatment: Place the surface-modified membrane obtained in step S3 in a glassware, then add a pentanediol solution with a mass fraction of 20% and heat it to 50 °C for crosslinking reaction. After 8 hours of crosslinking reaction, wash and dry to obtain the amino acid derivative polymer membrane material.

[0041] Example 4: A method for preparing an amino acid derivative polymer membrane material, in the S1 polymer solution preparation step, the mass concentration of the amino acid derivative is changed to 0.3 g / L; the mass ratio of the amino acid derivative to the polyether is changed to 1:1.2; the remaining preparation steps are the same as those in Example 3.

[0042] Example 5: A method for preparing an amino acid derivative polymer membrane material, in the S1 polymer solution preparation step, the mass concentration of the amino acid derivative is changed to 0.5 g / L; the mass ratio of the amino acid derivative to the polyether is changed to 1:1.5; the remaining preparation steps are the same as those in Example 3.

[0043] Example 6: A method for preparing an amino acid derivative polymer membrane material, in the S3 membrane surface modification step, the mass fraction of the mercaptoacetic acid solution is 3%; the remaining preparation steps are the same as those in Example 5.

[0044] Example 7: A method for preparing an amino acid derivative polymer membrane material, in the S3 membrane surface modification step, the mass fraction of the mercaptoacetic acid solution is 4%; the remaining preparation steps are the same as those in Example 5.

[0045] Example 8: A method for preparing an amino acid derivative polymer membrane material, in the S3 membrane surface modification step, the mass fraction of the mercaptoacetic acid solution is 5%; the remaining preparation steps are the same as those in Example 5.

[0046] Example 9: A method for preparing an amino acid derivative polymer membrane material, in the S3 membrane surface modification step, the mass fraction of the mercaptoacetic acid solution is 6%; the remaining preparation steps are the same as those in Example 5.

[0047] Example 10: A method for preparing an amino acid derivative polymer membrane material, in the S3 membrane surface modification step, the mass fraction of the chloroethylamine solution is 2%; the remaining preparation steps are the same as those in Example 6.

[0048] Example 11: A method for preparing an amino acid derivative polymer membrane material, in the S3 membrane surface modification step, the mass fraction of the chloroethylamine solution is 3%; the remaining preparation steps are the same as those in Example 6.

[0049] Example 12: A method for preparing an amino acid derivative polymer membrane material, remove the S4 crosslinking treatment step, and the remaining experimental step parameters are the same as those in Example 11.

[0050] Perform performance tests on the amino acid derivative polymer membrane materials prepared in Examples 1 to 12:

[0051] (1) Biocompatibility detection: Common cell lines (such as L929 mouse fibroblasts, HEK293 human kidney cells, etc.) were selected for culture. The amino acid derivative polymer membrane materials (membrane-like materials) prepared in different examples were co-cultured with cells for 24 hours, 48 hours, and 72 hours respectively. The cells were treated with MTT reagent, and the OD values of each group of cells were measured to reflect cell viability. The relative percentage of cell activity was calculated to compare the biocompatibility of different materials. The experimental results are shown in the following table:

[0052] Example Cell viability at 24 h (%) Cell viability at 48 h (%) Cell viability at 72 h (%) 1 85 90 93 2 88 93 95 3 90 94 97 4 91 94.5 97.7 5 92 95 98.2 6 93 96 99 7 91 95 98 8 90 92 95 9 89 90 93 10 94 97 99 11 91 93 95 12 83 80 77

[0053] From the data in the above table, it can be seen that the amino acid derivative polymer membrane materials of Examples 1 to 11 showed good biocompatibility in the cell activity experiment, and the cell activity was above 90%; as the concentration of amino acid derivatives in the material increased, the cell activity would also increase slightly; Example 12 was an amino acid derivative polymer membrane material prepared without cross-linking treatment, and the cell activity of this material decreased. Therefore, it can be obtained that the affinity of the material with a higher concentration of amino acid derivatives and after cross-linking treatment for cells will increase.

[0054] (2) Mechanical strength test: A universal material testing machine was used for tensile testing to measure the tensile strength and elongation at break of the membrane material. The membrane-like materials in different examples were selected and cut into samples of standard size (for example, 10 mm × 50 mm). The tensile speed was set at 1 mm / min, and the maximum tensile strength and elongation at break of the samples were recorded. The experimental results are shown in the following table:

[0055]

[0056]

[0057] From the data in the above table, it can be seen that the mechanical strength of Examples 1 to 11 increased with the increase in the concentration of amino acid derivatives and the strengthening of cross-linking treatment. Since Example 12 was not cross-linked, the mechanical properties of the prepared amino acid derivative polymer membrane material were poor.

[0058] (3) Stability detection: The prepared membrane samples were exposed to high temperature (80 °C), low temperature (-20 °C), and humidity environment (95% relative humidity) for 1 month. The mass change, surface morphology, and tensile strength change of the membrane material were measured. The experimental data are shown in the following table:

[0059] Example Mass loss (%) Change in tensile strength (%) Change in surface morphology 1 5 8 Slight cracks on the membrane surface 2 4.5 7 Slight swelling 3 4 6 No obvious change 4 3.5 5 No obvious change 5 3.2 4 No obvious change 6 3.0 3 No obvious change 7 3.1 4 No obvious change 8 3.2 5 No obvious change 9 3.3 6 No obvious change 10 2.9 2.5 No obvious change 11 3.1 4 No obvious change 12 10 15 Cracks on the membrane surface

[0060] From the experimental data in the above table, it can be seen that Examples 3 to 11 exhibit high stability, the stability of Examples 1 to 2 is average, and the stability of Example 12 is poor, among which Example 10 exhibits the best stability. Therefore, it shows that crosslinking treatment and modification of the membrane surface help to improve the stability of the membrane material.

[0061] (4) The experimental data of the selectivity and separation function detection are shown in the following table:

[0062]

[0063]

[0064] From the experimental data in the above table, it can be seen that the amino acid derivative polymer membrane materials prepared in Examples 1 to 12 all have good permeability and selectivity, indicating that modifying the membrane surface can optimize the separation function of the membrane. Among them, the performance of Examples 6 and 10 is the best, indicating that when the mass fraction of the mercaptoacetic acid solution is 3% and the mass fraction of the chloroethylamine solution is 2%, the surface modification effect of the membrane is the best, and the separation performance of the prepared membrane material is the best.

[0065] In summary, the amino acid derivative polymer membrane material prepared by the preparation method of the amino acid derivative polymer membrane material provided by the present invention has high separation performance and selectivity, and also has good biocompatibility, stability and mechanical properties. This technology can be widely applied to many fields such as biological separation, environmental purification, drug delivery, etc., and has significant innovation and practical value.

[0066] Obviously, the above examples are only examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A method for preparing an amino acid derivative polymer film material, characterized in that: The following steps are involved: S1 Preparation of polymer solution: Add the amino acid derivative to a reaction bottle, add a solvent to dissolve it, then add the polyether, stir and mix to dissolve it, add the initiator after all the dissolution is complete, control the reaction temperature and reaction time to carry out polymerization reaction, and cool after the reaction is completed to obtain a polymer solution; S2 film formation and deposition: the polymer solution obtained in step S1 is uniformly coated on a smooth plate, and a film is formed by spin coating. After coating, a heat treatment is performed, and the temperature and time of the heat treatment are controlled to obtain a film; S3: Surface modification of the membrane: soaking the membrane obtained in step S2 in a thioacetic acid solution, and then heating for reaction. After the reaction is completed, washing with deionized water, soaking in a chloroethylamine solution, and heating for reaction. After the reaction is completed, taking out the membrane, washing it with deionized water, and then placing it in a dryer for drying to obtain a surface-modified membrane. S4 cross-linking treatment: the surface modified membrane obtained in step S3 is placed in a glass container, and then a pentanediol solution is added and heated to cause a cross-linking reaction. After the cross-linking is completed, the amino acid derivative polymer membrane material is obtained by washing and drying.

2. The method for preparing an amino acid derivative polymer film material according to claim 1, characterized in that: In the step of preparing the polymer solution S1, the solvent is dimethyl sulfoxide.

3. The method for preparing an amino acid derivative polymer film material according to claim 1, characterized in that: In the step S1 of preparing the polymer solution, the mass concentration of the amino acid derivative is 0.1 to 0.5 g / L.

4. The method for preparing an amino acid derivative polymer film material according to claim 1, characterized in that: In the S1 polymer solution preparation step, the mass ratio of the amino acid derivative to the polyether is 1:(1-1.5).

5. The method for preparing an amino acid derivative polymer film material according to claim 1, characterized in that: In the step S1 of preparing the polymer solution, the polymerization reaction temperature is 80-120° C., and the reaction time is 2-4 hours.

6. The method for preparing an amino acid derivative polymer film material according to claim 1, characterized in that: In the step of forming and depositing the S2 film, the heat treatment temperature is 110-130° C. and the time is 0.5-3 h.

7. The method for preparing an amino acid derivative polymer film material according to claim 1, characterized in that: In the S2 film forming and deposition step, the film has a thickness of 10-50 μm.

8. The method for preparing an amino acid derivative polymer film material according to claim 1, characterized in that: In the surface modification step of the S3 membrane, the mass fraction of the mercaptoacetic acid solution is 2-6%; the mass fraction of the ethylamine chloride solution is 1-3%; and the drying temperature of the dryer is 60-70°C.

9. The method for preparing an amino acid derivative polymer film material according to claim 1, characterized in that: In the S4 cross-linking treatment, the mass fraction of the pentanediol solution is 10-20%; the temperature of the cross-linking reaction is 50-70° C., and the time of the cross-linking reaction is 3-6 hours.

10. An amino acid derivative polymer film material prepared by the method for preparing an amino acid derivative polymer film material according to any one of claims 1 to 9.

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