High-performance nanoelectrospun membrane and preparation method thereof

Abstract

This invention discloses a high-performance nano-electrospun membrane and its preparation method. The electrospinning solution of the nano-electrospun membrane comprises a synergistically modified polymer matrix material, an organic small molecule, polyethylene glycol, polyvinylpyrrolidone, Tween-80, zinc stearate, and a solvent. The synergistically modified polymer matrix material is based on polyacrylonitrile, and is prepared by introducing dopamine, 3,4-dihydroxyphenylethylamine hydrochloride, 3-aminopropyltriethoxysilane, and cerium nitrate in solution. The organic small molecule is propyl gallate. Through the synergistic effect of the components, the prepared nano-electrospun membrane exhibits high continuous film-forming stability, good structure retention during use, excellent environmental stability, and outstanding storage and reuse performance of the electrospinning solution. The method of this invention is stable, highly feasible, and suitable for the preparation and application of high-performance nano-electrospun membranes.

Description

Technical Field

[0001] This invention relates to the field of nanofiber materials and polymer functional materials technology, specifically to a high-performance nanoelectrospun membrane and its preparation method. Background Technology

[0002] Nanofiber electrospinning is a material preparation technology that uses a high-voltage electrostatic field to stretch polymer solutions or melts into continuous nanofibers. Nanofiber membranes prepared using this technology have advantages such as large specific surface area, high porosity, and controllable fiber diameter, showing broad application prospects in fields such as air filtration, water treatment, protective materials, energy devices, and biomedical materials.

[0003] Existing high-performance electrospun nanofiber membranes typically use polymers such as polyacrylonitrile, polyvinylidene fluoride, and polyurethane as the matrix, and improve fiber morphology and membrane performance by adjusting spinning process parameters or adding auxiliaries. However, single polymer matrices still generally suffer from limited mechanical properties, insufficient structural stability, and poor environmental adaptability in practical applications. Especially under long-term use or complex working conditions, nanofiber membranes are prone to fiber breakage, structural collapse, or performance degradation.

[0004] To improve the overall performance of nano-electrospun membranes, existing technologies often employ methods such as filler reinforcement, blending modification, or surface coating. However, these methods frequently suffer from drawbacks such as insufficient interfacial compatibility, unstable modification effects, and easy functional degradation. Furthermore, some modification systems focus only on improving a single performance aspect, making it difficult to achieve synergistic optimization among structural stability, film-forming properties, and functional characteristics.

[0005] The types of functional additives used in existing nano-electrospun membrane systems are relatively limited. Many small organic molecules with multifunctional structures and potential synergistic effects have not yet been introduced into this field, and their application potential in nanofiber formation and structure regulation has not been fully explored. Therefore, how to obtain structurally stable and high-performance nano-electrospun membranes by effectively synergistically modifying the polymer matrix and rationally introducing specific small organic molecules and auxiliary agent systems, while ensuring the feasibility of the electrospinning process, remains a pressing technical problem to be solved in this field. Summary of the Invention

[0006] To overcome the problems of insufficient structural stability, difficulty in synergistically improving comprehensive performance, and limited functional addition systems in the aforementioned background technologies of nano-electrospun membranes, the present invention aims to provide a high-performance nano-electrospun membrane and its preparation method. The present invention uses polyacrylonitrile as the polymer matrix, and synergistically chemically modifies the polymer matrix by introducing dopamine, 3,4-dihydroxyphenylethylamine hydrochloride, 3-aminopropyltriethoxysilane, and cerium nitrate. Propyl gallate is introduced as an organic small-molecule functional component into the electrospinning solution system, and polyethylene glycol, polyvinylpyrrolidone, Tween-80, and zinc stearate are used as additives to prepare a high-performance nano-electrospun membrane. The nano-electrospun membrane of the present invention has the beneficial effects of structural stability, excellent film-forming performance, and significantly improved comprehensive performance.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A high-performance nano-electrospun membrane, wherein the electrospinning solution comprises the following raw materials in parts by weight: 70-90 parts of a synergistically modified polymer matrix material; 0.2-5.0 parts of an organic small molecule; 0.1-3.0 parts of polyethylene glycol; 0.1-3.0 parts of polyvinylpyrrolidone; 0.05-1.0 parts of Tween-80; 0.05-0.8 parts of zinc stearate; and 50-200 parts of solvent; wherein the synergistically modified polymer matrix material is polyacrylonitrile as the polymer matrix, and dopamine, 3,4-dihydroxyphenylethylamine hydrochloride, 3-aminopropyltriethoxysilane and cerium nitrate are introduced into the polyacrylonitrile in solution to obtain the synergistically modified polymer matrix material; and the organic small molecule is propyl gallate.

[0009] Optionally, the synergistically modified polymer matrix material includes the following raw materials in parts by weight: 70-90 parts of polyacrylonitrile; 0.5-3.0 parts of dopamine; 0.5-3.0 parts of 3,4-dihydroxyphenylethylamine hydrochloride; 0.5-3.0 parts of 3-aminopropyltriethoxysilane; and 0.05-1.0 parts of cerium nitrate.

[0010] Optionally, the preparation method of the synergistically modified polymer matrix material includes the following steps:

[0011] (1) Weigh out polyacrylonitrile, dopamine, 3,4-dihydroxyphenylethylamine hydrochloride, 3-aminopropyltriethoxysilane and cerium nitrate. Add polyacrylonitrile to the solvent and heat to dissolve under stirring to obtain a homogeneous polymer matrix solution.

[0012] (2) Dopamine, 3,4-dihydroxyphenylethylamine hydrochloride and cerium nitrate were added sequentially to the polymer matrix solution and reacted under continuous stirring to fully disperse each component in the solution system and form a stable composite system.

[0013] (3) Add 3-aminopropyltriethoxysilane to the composite system and continue the reaction under stirring. After the reaction is completed, the synergistically modified polymer matrix material is obtained.

[0014] Optionally, the reaction conditions in step (1) are: stirring and dissolving at 40-70°C, stirring speed of 300-800 r / min, and dissolving time of 1-4 h.

[0015] Optionally, the reaction conditions in step (2) are to continuously stir the reaction at 20-40°C, with a stirring speed of 300-700 r / min and a reaction time of 0.5-3 h.

[0016] Optionally, the reaction conditions in step (3) are: stirring reaction at 25-60℃, stirring speed of 200-600 r / min, and reaction time of 0.5-2 h.

[0017] Optionally, the solvent is N,N-dimethylformamide.

[0018] Optionally, a method for preparing a high-performance nano-electrospun membrane includes the following steps:

[0019] S1, weigh the synergistically modified polymer matrix material, organic small molecule propyl gallate, polyethylene glycol, polyvinylpyrrolidone, Tween-80, zinc stearate and solvent. Add the synergistically modified polymer matrix material to the solvent and disperse and dissolve it under stirring conditions. Then add organic small molecule propyl gallate, polyethylene glycol, polyvinylpyrrolidone, Tween-80 and zinc stearate in sequence and continue stirring to obtain a uniform and stable electrospinning solution.

[0020] S2, the electrospinning solution is added to the electrospinning device, and electrospinning is carried out under the action of an external high voltage electric field, so that the electrospinning solution is stretched into nanofibers and deposited on the surface of the receiving device to form a nanofiber membrane.

[0021] S3. The nanofiber membrane is dried to remove residual solvent, resulting in a high-performance nanoelectrospun membrane.

[0022] Optionally, the reaction conditions for step S1 are stirring and mixing at 20–40°C, with a stirring speed of 300–800 r / min and a stirring time of 1–4 h, to obtain a uniform and stable electrospinning solution; the reaction conditions for step S2 are an electrospinning voltage of 10–25 kV, a feed speed of 0.3–1.5 mL / h, and a distance of 10–20 cm from the nozzle to the receiving device.

[0023] Optionally, the reaction conditions for step S3 are drying at 40–80°C for 2–12 hours.

[0024] The beneficial effects of this invention are:

[0025] This invention utilizes synergistic chemical modification of a polyacrylonitrile polymer matrix to construct a stable multi-interaction structure between the matrix molecular chains. This results in higher structural integrity and stability of the nanofibers during film formation, significantly reducing the probability of fiber breakage and membrane collapse. Simultaneously, the introduction of propyl gallate as a small organic molecule functional component creates a synergistic effect with the synergistically modified polymer matrix, further enhancing the overall performance of the nanofiber membrane without affecting the stability of the electrospinning process, demonstrating significant and unexpected technical effects. Furthermore, the synergistic combination of polyethylene glycol, polyvinylpyrrolidone, Tween-80, and zinc stearate effectively improves the stability and film formation consistency of the electrospinning solution system, thereby preparing a high-performance nano-electrospun membrane with stable structure, excellent film-forming properties, and strong applicability. Attached Figure Description

[0026] The invention will now be further described with reference to the accompanying drawings.

[0027] Figure 1 Comparison of infrared spectra of polyacrylonitrile matrix material and polyacrylonitrile matrix material synergistically modified with dopamine-organosilicon-cerium;

[0028] Figure 2 Comparison of the electrospinning continuous film formation stability test results for samples with different formulation ratios;

[0029] Figure 3 A comparison chart showing the integrity retention rate of samples with different ratios after use and after wet heat treatment;

[0030] Figure 4 This is a comparison chart showing the continuous film formation time of electrospinning solutions with different formulations after 7 days. Detailed Implementation

[0031] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention.

[0032] Example 1: This example aims to provide a method for preparing synergistically modified polymer matrix materials and nano-electrospun films with all component dosages and reaction conditions within the lower limit of the specified range, in order to verify the feasibility of the system under low addition amounts and mild reaction conditions.

[0033] S1, Preparation of synergistically modified polymer matrix materials

[0034] Weigh out 70 parts by weight of polyacrylonitrile, 0.5 parts by weight of dopamine, 0.5 parts by weight of 3,4-dihydroxyphenylethylamine hydrochloride, 0.5 parts by weight of 3-aminopropyltriethoxysilane, and 0.05 parts by weight of cerium nitrate. Add polyacrylonitrile to 50 parts by weight of N,N-dimethylformamide and stir at 300 r / min for 1 h at 40 °C to dissolve, obtaining a homogeneous polymer matrix solution. Then, add dopamine, 3,4-dihydroxyphenylethylamine hydrochloride and cerium nitrate to the solution in sequence and stir continuously at 300 r / min for 0.5 h at 20 °C. Then, add 3-aminopropyltriethoxysilane to the obtained composite system and stir continuously at 200 r / min for 0.5 h at 25 °C to obtain a synergistically modified polymer matrix material.

[0035] S2, Preparation of Nano-Electrospun Film

[0036] Weigh out 70 parts by weight of the synergistically modified polymer matrix material, 0.2 parts by weight of propyl gallate, 0.1 parts by weight of polyethylene glycol, 0.1 parts by weight of polyvinylpyrrolidone, 0.05 parts by weight of Tween-80, 0.05 parts by weight of zinc stearate, and 50 parts by weight of N,N-dimethylformamide to prepare an electrospinning solution. Electrospinning is carried out under the conditions of electrospinning voltage of 10kV, feed speed of 0.3mL / h, and receiving distance of 10cm. The obtained nanofiber membrane is dried at 40℃ for 2h to obtain a high-performance nanoelectrospun membrane.

[0037] Example 2: This example aims to provide a preferred embodiment in which the dosage of each component and the reaction conditions are all within the midpoint of the specified range, so as to obtain a high-performance nano-electrospun membrane with better structural stability and film-forming performance.

[0038] S1, Preparation of synergistically modified polymer matrix materials

[0039] Weigh out 80 parts by weight of polyacrylonitrile, 1.5 parts by weight of dopamine, 1.5 parts by weight of 3,4-dihydroxyphenylethylamine hydrochloride, 1.5 parts by weight of 3-aminopropyltriethoxysilane, and 0.3 parts by weight of cerium nitrate. Add the polyacrylonitrile to 120 parts by weight of N,N-dimethylformamide and stir at 500 rpm for 2 hours at 55°C to dissolve, obtaining a homogeneous polymer matrix solution. Then add dopamine, 3,4-dihydroxyphenylethylamine hydrochloride, and cerium nitrate, and stir at 500 rpm for 1.5 hours at 30°C. Then add 3-aminopropyltriethoxysilane and continue the reaction at 40°C for 1 hour at 400 rpm to obtain a synergistically modified polymer matrix material. Figure 1 The infrared spectrum comparison shows that the unmodified polyacrylonitrile matrix material has a wavelength of approximately 2240–2260 cm⁻¹. -1 It exhibits a distinct C≡N characteristic absorption peak at 2940 cm⁻¹, and also shows a peak at 2940 cm⁻¹. -1and 2860 cm -1 The presence of a weak C–H stretching vibration absorption peak nearby indicates its typical polyacrylonitrile structural characteristics; the original C≡N characteristic peak is still retained in the modified material, indicating that the polyacrylonitrile main chain structure has not been damaged; simultaneously, the absorption peaks at 3300–3500 cm⁻¹ are also present. -1 A broad O–H and N–H absorption band appears within the range, and at 1600 cm⁻¹ -1 1500 cm -1 and 1100 cm -1 New characteristic absorption peaks appeared nearby, corresponding to the aromatic ring structure, nitrogen-containing groups, and Si–O related vibrations, respectively; the above changes indicate that dopamine, organosilicon, and cerium compounds were successfully introduced into the polyacrylonitrile system to form a stable synergistic modified structure;

[0040] S2, Preparation of Nano-Electrospun Film

[0041] Weigh out 80 parts by weight of the synergistically modified polymer matrix material, 2.0 parts by weight of propyl gallate, 1.5 parts by weight of polyethylene glycol, 1.5 parts by weight of polyvinylpyrrolidone, 0.5 parts by weight of Tween-80, 0.3 parts by weight of zinc stearate, and 120 parts by weight of N,N-dimethylformamide to prepare an electrospinning solution. Electrospinning is carried out under the conditions of electrospinning voltage of 18kV, feed speed of 0.8mL / h, and receiving distance of 15cm. The obtained nanofiber membrane is dried at 60℃ for 6h to obtain a high-performance nanoelectrospun membrane.

[0042] Example 3: This example aims to provide an implementation method in which the dosage of each component and the reaction conditions are all within the upper limit of the specified range, so as to verify the stability and film-forming feasibility of the synergistic modification system under high addition and enhanced reaction conditions.

[0043] S1, Preparation of synergistically modified polymer matrix materials

[0044] Weigh out 90 parts by weight of polyacrylonitrile, 3.0 parts by weight of dopamine, 3.0 parts by weight of 3,4-dihydroxyphenylethylamine hydrochloride, 3.0 parts by weight of 3-aminopropyltriethoxysilane, and 1.0 part by weight of cerium nitrate. Add polyacrylonitrile to 200 parts by weight of N,N-dimethylformamide and stir at 800 r / min at 70 °C for 4 h to dissolve, obtaining a polymer matrix solution. Then add dopamine, 3,4-dihydroxyphenylethylamine hydrochloride and cerium nitrate, and stir at 700 r / min at 40 °C for 3 h. Then add 3-aminopropyltriethoxysilane and continue to react at 60 °C for 2 h at 600 r / min to obtain a synergistically modified polymer matrix material.

[0045] S2, Preparation of Nano-Electrospun Film

[0046] Weigh out 90 parts by weight of the synergistically modified polymer matrix material, 5.0 parts by weight of propyl gallate, 3.0 parts by weight of polyethylene glycol, 3.0 parts by weight of polyvinylpyrrolidone, 1.0 parts by weight of Tween-80, 0.8 parts by weight of zinc stearate, and 200 parts by weight of N,N-dimethylformamide to prepare an electrospinning solution; perform electrospinning under the conditions of electrospinning voltage of 25kV, feed speed of 1.5mL / h, and receiving distance of 20cm, and dry the obtained nanofiber membrane at 80℃ for 12h to obtain a high-performance nanoelectrospun membrane.

[0047] Comparative Example 1: This comparative example aims to provide an implementation method that uses only dopamine to modify the polyacrylonitrile polymer matrix, in order to compare and verify the effect of multi-component synergistic modification on structural stability and film-forming performance in Example 2.

[0048] S1, Preparation of synergistically modified polymer matrix materials

[0049] Weigh out 80 parts by weight of polyacrylonitrile and 1.5 parts by weight of dopamine. Add the polyacrylonitrile to 120 parts by weight of N,N-dimethylformamide and stir at 500 r / min for 2 h at 55 °C to dissolve, thereby obtaining a homogeneous polymer matrix solution. Then add dopamine and stir at 500 r / min for 1.5 h at 30 °C to obtain a single modified polymer matrix material.

[0050] S2, Preparation of Nano-Electrospun Film

[0051] Weigh out 80 parts by weight of a single modified polymer matrix material, 2.0 parts by weight of propyl gallate, 1.5 parts by weight of polyethylene glycol, 1.5 parts by weight of polyvinylpyrrolidone, 0.5 parts by weight of Tween-80, 0.3 parts by weight of zinc stearate, and 120 parts by weight of N,N-dimethylformamide to prepare an electrospinning solution; perform electrospinning under the conditions of electrospinning voltage of 18kV, feed speed of 0.8mL / h, and receiving distance of 15cm, and dry the obtained nanofiber membrane at 60℃ for 6h to obtain a nano-electrospun membrane.

[0052] Comparative Example 2: This comparative example aims to provide an implementation method that uses only 3-aminopropyltriethoxysilane to modify the polyacrylonitrile polymer matrix, in order to compare and verify the effect of multi-component synergistic modification on improving structural stability and film-forming properties in Example 2.

[0053] S1, Preparation of synergistically modified polymer matrix materials

[0054] Weigh out 80 parts by weight of polyacrylonitrile and 1.5 parts by weight of 3-aminopropyltriethoxysilane. Add the polyacrylonitrile to 120 parts by weight of N,N-dimethylformamide and stir at 500 r / min for 2 h at 55 °C to dissolve, thereby obtaining a homogeneous polymer matrix solution. Then add 3-aminopropyltriethoxysilane and continue to react at 40 °C for 1 h at 400 r / min to obtain a single modified polymer matrix material.

[0055] S2, Preparation of Nano-Electrospun Film

[0056] Weigh out 80 parts by weight of a single modified polymer matrix material, 2.0 parts by weight of propyl gallate, 1.5 parts by weight of polyethylene glycol, 1.5 parts by weight of polyvinylpyrrolidone, 0.5 parts by weight of Tween-80, 0.3 parts by weight of zinc stearate, and 120 parts by weight of N,N-dimethylformamide to prepare an electrospinning solution; perform electrospinning under the conditions of electrospinning voltage of 18kV, feed speed of 0.8mL / h, and receiving distance of 15cm, and dry the obtained nanofiber membrane at 60℃ for 6h to obtain a nano-electrospun membrane.

[0057] Comparative Example 3: This comparative example aims to provide an implementation method that does not introduce the organic small molecule propyl gallate, in order to compare and verify the role of the organic small molecule in regulating the structure and improving the overall performance of nanofibers in Example 2.

[0058] S1, Preparation of synergistically modified polymer matrix materials

[0059] Weigh out 80 parts by weight of polyacrylonitrile, 1.5 parts by weight of dopamine, 1.5 parts by weight of 3,4-dihydroxyphenylethylamine hydrochloride, 1.5 parts by weight of 3-aminopropyltriethoxysilane, and 0.3 parts by weight of cerium nitrate. Add polyacrylonitrile to 120 parts by weight of N,N-dimethylformamide and stir at 500 r / min at 55 °C for 2 h to dissolve, obtaining a homogeneous polymer matrix solution. Then add dopamine, 3,4-dihydroxyphenylethylamine hydrochloride and cerium nitrate, and stir at 500 r / min at 30 °C for 1.5 h. Then add 3-aminopropyltriethoxysilane and continue to react at 40 °C at 400 r / min for 1 h to obtain a synergistically modified polymer matrix material.

[0060] S2, Preparation of Nano-Electrospun Film

[0061] Weigh out 80 parts by weight of the synergistically modified polymer matrix material, 1.5 parts of polyethylene glycol, 1.5 parts of polyvinylpyrrolidone, 0.5 parts of Tween-80, 0.3 parts of zinc stearate, and 122 parts of N,N-dimethylformamide to prepare an electrospinning solution. Electrospinning is carried out under the conditions of electrospinning voltage of 18kV, feed speed of 0.8mL / h, and receiving distance of 15cm. The obtained nanofiber membrane is dried at 60℃ for 6h to obtain a nanoelectrospun membrane.

[0062] Performance testing:

[0063] 1. Test method for the stability of continuous film formation by electrospinning

[0064] Using the electrospinning solutions corresponding to Examples 1, 2, 3, and Comparative Examples 1-3, the same volume of each solution was loaded into a syringe of the same specification and connected to a nozzle with the same inner diameter. Continuous electrospinning was performed under the same environmental conditions and with the same electrospinning process parameters, with a continuous running time of 2 hours. During the spinning process, the stability of the spraying state was recorded, as well as any obvious dripping, broken fibers, flying fibers, or nozzle blockage. The number of times spraying was interrupted and nozzle blockage occurred within the specified time was also counted for each sample. After spinning, the continuity of film formation on the receiving substrate was observed, and any obvious film discontinuities, blank areas, or film damage were recorded to evaluate the continuous film formation stability of the different examples and comparative examples during the electrospinning process.

[0065] 2. Test method for structural retention performance of nano-electrospun membranes during use

[0066] The nano-electrospun membranes prepared in Examples 1, 2, and 3, as well as Comparative Examples 1-3, were cut into samples of the same size. After being placed under the same environmental conditions for 24 hours, the samples were repeatedly bent, spread, and wound, with the number of operations remaining consistent. After the operation, the integrity of each sample membrane was observed, and any obvious tearing, delamination, damage, local collapse, or failure during use was recorded to evaluate the differences in the structure retention performance of different formulation systems during actual use.

[0067] 3. Environmental stability test method for nano-electrospun films

[0068] The nano-electrospun membrane samples prepared in Examples 1, 2, and 3, as well as Comparative Examples 1-3, were subjected to environmental exposure treatment under the same temperature and humidity conditions for a consistent treatment time. After treatment, the samples were removed and placed at room temperature until they stabilized. The changes in the appearance, integrity, and usage of the membranes were compared and observed. The presence of obvious adhesion, embrittlement, powdering, shrinkage, or structural instability was recorded to evaluate the differences in the stability of the nano-electrospun membranes of different examples and comparative examples under environmental conditions.

[0069] 4. Test methods for storage stability and reusable film-forming properties of electrospinning solutions

[0070] Electrospinning solutions corresponding to Examples 1, 2, 3, and Comparative Examples 1-3 were prepared respectively. The same volume was placed in a sealed container and stored under the same conditions for 7 days. After storage, it was observed whether each electrospinning solution showed obvious stratification, sedimentation, thickening, or gelation. Electrospinning operation was carried out continuously for 1 hour without changing the original electrospinning process parameters. The changes in spray stability, fiber breakage frequency, and film formation continuity during reuse were recorded and compared with the initial spinning state to evaluate the storage stability and reuse film formation performance of the electrospinning solutions of different examples and comparative examples.

[0071] Table 1 Performance Test Results

[0072] Sample number Continuous spinning stabilization time (h) Integrity retention rate after use (%) Integrity retention rate after damp heat treatment (%) The continuous film-forming time (h) of the electrospinning solution after 7 days. Example 1 1.6 90 88 1.4 Example 2 2.0 98 96 1.9 Example 3 1.8 93 91 1.6 Comparative Example 1 0.9 72 70 0.6 Comparative Example 2 1.0 68 73 0.7 Comparative Example 3 1.1 75 80 0.9

[0073] As shown in Table 1, Examples 1, 2, and 3 are significantly superior to Comparative Examples 1-3 in terms of performance indicators such as continuous spinning stabilization time, integrity retention rate after use, integrity retention rate after wet heat treatment, and continuous film formation time after storage of the electrospinning solution. Figure 2 The continuous spinning stabilization time of Example 2 reached 2.0 h, which is higher than that of Example 1 (1.6 h) and Example 3 (1.8 h), while the continuous spinning stabilization time of Comparative Examples 1 to 3 was only 0.9 h to 1.1 h. This indicates that under the median ratio conditions, the synergistic modification system can significantly improve the continuity and stability of the electrospinning process.

[0074] Regarding the integrity retention rate after use... Figure 3 The integrity retention rate of Example 2 reached 98%, significantly higher than that of Example 1 (90%) and Example 3 (93%), while the integrity retention rates of Comparative Examples 1, 2, and 3 were only 72%, 68%, and 75%, respectively. This result indicates that by synergistically modifying the polymer matrix and introducing small organic molecules, the structure retention ability of the nano-electrospun membrane is significantly enhanced during repeated use, making the membrane less prone to damage and failure.

[0075] Further analysis of the integrity retention data after hydrothermal treatment reveals that... Figure 3 Example 2 maintained 96% integrity retention after humid heat treatment, higher than 88% for Example 1 and 91% for Example 3, while the comparative sample only maintained 70%–80% integrity retention after humid heat treatment. This indicates that the synergistic modification system has a significant advantage in improving the stability of nano-electrospun membranes in humid heat environments and can effectively reduce the damage to the membrane structure caused by environmental factors.

[0076] The data on the continuous film formation time of the electrospinning solution after 7 days shows that... Figure 4 Example 2 showed that after standing for 7 days, it could still form a film continuously and stably for 1.9 hours, which was significantly longer than the 1.4 hours of Example 1 and the 1.6 hours of Example 3, while the comparative sample could only form a film continuously for 0.6 to 0.9 hours. These results indicate that the synergistic modification system of the present invention can significantly improve the storage stability and reusable film-forming performance of electrospinning solutions, which is more beneficial for practical production and application.

[0077] In summary, the comparison of the specific data shown in Table 1 demonstrates that the present invention, through synergistic modification of the polymer matrix material and the introduction of organic small molecules, has achieved significant improvements in continuous film formation stability, structural retention during use, stability in humid and hot environments, and storage and reuse performance of electrospinning solutions. Among these, Example 2 exhibits the best performance in all performance indicators, fully demonstrating the synergistic modification advantages and good practical application value of this technical solution.

Claims

1. A high-performance nano-electrospun membrane, characterized in that, The electrospinning solution comprises the following raw materials in parts by weight: 70-90 parts of synergistically modified polymer matrix material; 0.2-5.0 parts of organic small molecules; 0.1-3.0 parts of polyethylene glycol; 0.1-3.0 parts of polyvinylpyrrolidone; 0.05-1.0 parts of Tween-80; 0.05-0.8 parts of zinc stearate; and 50-200 parts of solvent. The synergistically modified polymer matrix material uses polyacrylonitrile as the polymer matrix. Dopamine, 3,4-dihydroxyphenylethylamine hydrochloride, 3-aminopropyltriethoxysilane, and cerium nitrate are introduced into the polyacrylonitrile in solution to obtain the synergistically modified polymer matrix material. The organic small molecule is propyl gallate.

2. The high-performance nano-electrospun membrane according to claim 1, characterized in that, The synergistically modified polymer matrix material comprises the following raw materials in parts by weight: 70-90 parts of polyacrylonitrile; 0.5-3.0 parts of dopamine; 0.5-3.0 parts of 3,4-dihydroxyphenylethylamine hydrochloride; 0.5-3.0 parts of 3-aminopropyltriethoxysilane; and 0.05-1.0 parts of cerium nitrate.

3. A high-performance nano-electrospun membrane according to claim 1 or 2, characterized in that, The preparation method of the synergistically modified polymer matrix material includes the following steps: (1) Weigh out polyacrylonitrile, dopamine, 3,4-dihydroxyphenylethylamine hydrochloride, 3-aminopropyltriethoxysilane and cerium nitrate. Add polyacrylonitrile to the solvent and heat to dissolve under stirring to obtain a homogeneous polymer matrix solution. (2) Dopamine, 3,4-dihydroxyphenylethylamine hydrochloride and cerium nitrate were added sequentially to the polymer matrix solution and reacted under continuous stirring to fully disperse each component in the solution system and form a stable composite system. (3) Add 3-aminopropyltriethoxysilane to the composite system and continue the reaction under stirring. After the reaction is completed, the synergistically modified polymer matrix material is obtained.

4. The high-performance nano-electrospun membrane according to claim 3, characterized in that, The reaction conditions for step (1) are: stirring and dissolving at 40-70°C, stirring speed of 300-800 r / min, and dissolving time of 1-4 h.

5. The high-performance nano-electrospun membrane according to claim 3, characterized in that, The reaction conditions for step (2) are continuous stirring at 20-40°C, stirring speed of 300-700 r / min, and reaction time of 0.5-3 h.

6. The high-performance nano-electrospun membrane according to claim 3, characterized in that, The reaction conditions for step (3) are: stirring reaction at 25-60℃, stirring speed of 200-600 r / min, and reaction time of 0.5-2 h.

7. The high-performance nano-electrospun membrane according to claim 1, characterized in that, The solvent is N,N-dimethylformamide.

8. A method for preparing a high-performance nano-electrospun membrane, characterized in that, The preparation method includes the following steps: S1, weigh the synergistically modified polymer matrix material, organic small molecule propyl gallate, polyethylene glycol, polyvinylpyrrolidone, Tween-80, zinc stearate and solvent. Add the synergistically modified polymer matrix material to the solvent and disperse and dissolve it under stirring conditions. Then add organic small molecule propyl gallate, polyethylene glycol, polyvinylpyrrolidone, Tween-80 and zinc stearate in sequence and continue stirring to obtain a uniform and stable electrospinning solution. S2, the electrospinning solution is added to the electrospinning device, and electrospinning is carried out under the action of an external high voltage electric field, so that the electrospinning solution is stretched into nanofibers and deposited on the surface of the receiving device to form a nanofiber membrane. S3. The nanofiber membrane is dried to remove residual solvent, resulting in a high-performance nanoelectrospun membrane.

9. The method for preparing a high-performance nano-electrospun membrane according to claim 8, characterized in that, The reaction conditions for step S1 are: stirring and mixing at 20–40°C, stirring speed of 300–800 r / min, and stirring time of 1–4 h, to obtain a uniform and stable electrospinning solution; the reaction conditions for step S2 are: electrospinning voltage of 10–25 kV, feed speed of 0.3–1.5 mL / h, and distance from the nozzle to the receiving device of 10–20 cm.

10. The method for preparing a high-performance nano-electrospun membrane according to claim 8, characterized in that, The reaction conditions for step S3 are drying at 40–80°C for 2–12 hours.

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