Two-dimensional honeycomb and three-dimensional spine-shaped double-coupling microstructure nanofiber membrane, and preparation method and application thereof

Abstract

The application relates to the technical field of nanofiber membranes, in particular to a two-dimensional honeycomb and three-dimensional spinous double-coupling microstructure nanofiber membrane and a preparation method and application thereof, which comprises the following steps: step 1, thermoplastic polyurethane (TPU) is dissolved in an organic solvent, and homogeneous spinning liquid is obtained after heating and stirring; step 2, a foam template is subjected to oxygen plasma treatment, so that the surface of the foam template presents a negative potential; step 3, the homogeneous spinning liquid is injected into a syringe, electrospinning is carried out under a high-voltage electrostatic field with the foam serving as a collector, the flow rate of the spinning liquid is controlled through a propelling pump, the nanofiber membrane is peeled off from the surface of the foam after spinning is completed, and drying is carried out, so that the two-dimensional honeycomb and three-dimensional spinous double-coupling microstructure nanofiber membrane is obtained. The double-coupling microstructure introduced in the application makes the maximum tensile strain of the nanofiber membrane increased by 77%, the maximum tensile stress increased by 88%, and the residual strain and the residual stress after 100 cycles of tensile stretching reduced by 27% and 34% respectively.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nanofiber membranes, in particular to a two-dimensional honeycomb and three-dimensional spinous double-coupling microstructure nanofiber membrane and a preparation method and application thereof. BACKGROUND

[0002] At present, with the rapid development of wearable bioelectronic technology, flexible nanofiber membranes with high tensile mechanical properties have become a research hotspot. In the prior art, patent CN202411484317.7 proposes a new type of nanofiber membrane prepared by a static electrospinning-static electro-spraying composite method, but is limited by the stress concentration effect of the two-dimensional random nanofiber network, and has problems of dynamic response lag and insufficient mechanical durability. Patent CN202411079484.3 uses a polyvinylidene fluoride-based mixed solution phase separation method to prepare a two-dimensional coupling microstructure nanofiber membrane, but the maximum tensile strain is less than 30%.

[0003] The root cause of the above technical bottleneck lies in the random and disordered distribution characteristics of the traditional electrospun nanofiber membrane, which leads to the performance game between the mechanical tensile properties and the cyclic tensile properties of the existing nanofiber membranes. Therefore, developing nanofiber membranes with cross-scale ordered microstructures to realize the synergistic optimization of mechanical tensile and cyclic mechanical properties is a key direction to break through the barriers of the existing technology. SUMMARY

[0004] The purpose of the present application is to solve the problems existing in the prior art, and a two-dimensional honeycomb and three-dimensional spinous double-coupling microstructure nanofiber membrane and a preparation method and application thereof are proposed. The nanofiber membrane prepared has cross-scale ordered microstructures and can realize the synergistic optimization of mechanical tensile and cyclic mechanical properties.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A preparation method of a two-dimensional honeycomb and three-dimensional spinous double-coupling microstructure nanofiber membrane, comprising the following steps:

[0007] Step 1: Dissolve thermoplastic polyurethane (TPU) in an organic solvent, and after heating and stirring, obtain a homogeneous spinning solution;

[0008] Step 2: Perform oxygen plasma treatment on the foam template to make the surface present a negative potential;

[0009] Step 3: Inject the homogeneous spinning solution into a syringe, use the foam as a collector, and perform electrospinning under a high-voltage electrostatic field. The flow rate of the spinning solution is controlled by a push pump. After the spinning is completed, the nanofiber membrane is peeled off from the surface of the foam and dried to obtain a two-dimensional honeycomb and three-dimensional spinous double-coupling microstructure nanofiber membrane.

[0010] Preferably, in step 1, the organic solvent is selected from any one or more of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); the mass ratio of thermoplastic polyurethane to organic solvent is 1:5 to 20, the heating temperature is 70 to 100°C, and the stirring time is 12 to 24 hours.

[0011] Preferably, in step 2, the foam template is selected from any one of polyurethane foam, polystyrene foam, polyethylene foam, polypropylene foam, silicone foam, melamine foam, polyethersulfone foam, and polyimide foam; the power of the oxygen plasma treatment is 1000-1500W, the treatment time is 40-90 seconds, and the surface potential of the foam is -1kV to -2.5kV.

[0012] Preferably, in step 3, the voltage of the high-voltage electrostatic field is 15–30 kV, the distance between the foam and the syringe needle tip is 15–25 cm, the spinning solution flow rate is 0.1–2.5 mL / h, and the drying time is 12–24 hours. During electrospinning, the spinning solution forms nanofibers under the action of the high-voltage electrostatic field and deposits on the surface of the foam template, forming a two-dimensional honeycomb and three-dimensional spiky dual-coupled microstructure.

[0013] The present invention also provides a two-dimensional honeycomb and three-dimensional spiky protrusion dual-coupled microstructure nanofiber membrane prepared by the above preparation method. The nanofiber membrane has a cross-scale ordered microstructure, including a two-dimensional honeycomb network and three-dimensional spiky protrusions.

[0014] Preferably, the nanofiber membrane has a maximum tensile strain of 200%, a maximum tensile stress of 28.7 MPa, and a residual strain of 5.14% after 100 cycles of tensile testing.

[0015] Application of a two-dimensional honeycomb and three-dimensional spiky dual-coupled microstructure nanofiber membrane prepared by the above preparation method in flexible electronic devices, sensors, filter materials or biomedical materials.

[0016] A flexible electronic device comprising a nanofiber membrane with a dual-coupled microstructure of two-dimensional honeycomb and three-dimensional spike-like structures.

[0017] A sensor comprising a nanofiber membrane with a dual-coupled microstructure of two-dimensional honeycomb and three-dimensional spike-like structures.

[0018] A filter material comprising a nanofiber membrane with a dual-coupled microstructure of two-dimensional honeycomb and three-dimensional spiky structures.

[0019] A biomedical material comprising a nanofiber membrane with a dual-coupled microstructure of two-dimensional honeycomb and three-dimensional spiny protrusions.

[0020] By employing the above technical solution—using thermoplastic polyurethane (TPU) as the electrospinning substrate material and negatively charged foam as a collecting plate—positively charged TPU nanofibers preferentially adsorb and deposit on the surface of the foam skeleton under a high-voltage electrostatic field, forming a two-dimensional honeycomb nanofiber membrane. With increasing deposition, a three-dimensional spiky microstructure further forms on the surface of the two-dimensional honeycomb structure, thus constructing a dual-coupled microstructure system of two-dimensional honeycomb and three-dimensional spiky structures. Compared with traditional two-dimensional electrospinned nanofiber membranes, the dual-coupled microstructure introduced in this invention increases the maximum tensile strain of the nanofiber membrane by 77%, increases the maximum tensile stress by 88%, and reduces the residual strain and residual stress by 27% and 34%, respectively, after 100 cycles of tensile testing.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. The two-dimensional honeycomb and three-dimensional spiky dual-coupled microstructure nanofiber membrane prepared by this invention has excellent mechanical properties, with a 77% increase in maximum tensile strain, an 88% increase in maximum tensile stress, and a 27% and 34% reduction in residual strain and residual stress after 100 cycles of tensile testing, respectively.

[0023] 2. The preparation method of this invention is simple, easy to operate, and low in cost, making it suitable for large-scale production.

[0024] 3. This invention solves the performance bottleneck of traditional electrospun nanofiber membranes through dual-coupling microstructure design, providing a new technical path for developing nanofiber membranes with excellent mechanical properties, and has broad application prospects in fields such as medical and health monitoring and human-computer interaction. Attached Figure Description

[0025] Figure 1 This is a flowchart illustrating the preparation process of the dual-coupled microstructure nanofiber membrane of the present invention.

[0026] Figure 2 The images show scanning electron microscope (SEM) images of conventional randomly distributed nanofiber membranes and dual-coupled microstructure nanofiber membranes, as well as optical images and three-dimensional contour maps of the three-dimensional spiky microstructures of the present invention.

[0027] Figure 3 The diagram shows a comparison of the maximum tensile mechanical properties of the dual-coupled microstructure nanofiber membrane of this invention and the traditional randomly distributed nanofiber membrane, as well as the residual strain and residual stress after 100 cycles of tensile testing. Detailed Implementation

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, so that those skilled in the art can better understand the advantages and features of the present invention, thereby making a clearer definition of the scope of protection of the present invention. The embodiments described in this invention are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0029] Example 1

[0030] Thermoplastic polyurethane and dimethylformamide were mixed at a mass ratio of 1:10 and heated and stirred at 80°C for 18 hours to obtain a homogeneous spinning solution. Polyurethane foam was selected as a template and treated with an oxygen plasma treatment instrument at 1200W power for 60 seconds to induce a negative potential of -1.8kV on the foam surface. The prepared spinning solution was injected into a syringe, and spinning was performed using a high-voltage electrostatic field with a voltage set to 20kV. The foam template served as a collector, positioned 20cm from the syringe needle tip, and the spinning solution flow rate was controlled at 0.5mL / h. After spinning, the nanofiber membrane was peeled off from the foam surface and dried in a fume hood for 18 hours to obtain a two-dimensional honeycomb and three-dimensional spiky dual-coupled microstructure nanofiber membrane.

[0031] Figure 1 This is a flowchart of the preparation process of dual-coupled microstructure nanofiber membranes; Figure 2 The images show a comparison of the appearance of the dual-coupled microstructure nanofiber membrane and the dual-coupled microstructure nanofiber membrane. (a) is a traditional randomly distributed nanofiber membrane; (b) is a two-dimensional honeycomb structure nanofiber membrane; (c) is a three-dimensional spiky microstructure on the surface of the two-dimensional honeycomb structure nanofiber membrane; and (d) is a three-dimensional outline of the dual-coupled microstructure nanofiber membrane. It can be seen that the height of the three-dimensional spiky microstructure is 5-15 micrometers. This demonstrates that the dual-coupled microstructure nanofiber membrane of the present invention successfully prepared a two-dimensional honeycomb structure and a three-dimensional spiky microstructure on its surface.

[0032] Example 2

[0033] Thermoplastic polyurethane and N-methylpyrrolidone were mixed at a mass ratio of 1:15 and heated and stirred at 90°C for 24 hours to obtain a homogeneous spinning solution. Polystyrene foam was selected as a template and treated with an oxygen plasma generator at 1500W power for 90 seconds to induce a negative potential of -2.5kV on the foam surface. The prepared spinning solution was injected into a syringe, and spinning was performed using a high-voltage electrostatic field with a voltage set to 25kV. The foam template served as a collector, positioned 25cm from the syringe needle tip, and the spinning solution flow rate was controlled at 1.0mL / h. After spinning, the nanofiber membrane was peeled off the foam surface and dried in a fume hood for 24 hours to obtain a nanofiber membrane with a two-dimensional honeycomb and three-dimensional spiky dual-coupled microstructure.

[0034] like Figure 3 As shown, Figure 3 The mechanical test diagrams of the dual-coupled microstructure nanofiber membrane obtained in Example 2 are shown. (a) is the stress-strain diagram under maximum tension; (b) is a comparison diagram of residual strain and residual stress after 100 cycles of tension. The results show that the performance of maximum tensile strain and stress, as well as residual strain and residual stress after 100 cycles of tension, is not as good as that of Example 1, but is worse than that of the randomly distributed nanofiber membrane obtained by conventional electrospinning.

[0035] Example 3

[0036] Thermoplastic polyurethane and tetrahydrofuran were mixed at a mass ratio of 1:5 and heated and stirred at 70°C for 12 hours to obtain a homogeneous spinning solution. Polyethylene foam was selected as a template and treated with an oxygen plasma treatment instrument at 1000W power for 40 seconds to induce a negative potential of -1.0kV on the foam surface. The prepared spinning solution was injected into a syringe, and spinning was performed using a high-voltage electrostatic field with a voltage set to 15kV. The foam template served as a collector, positioned 15cm from the syringe needle tip, and the spinning solution flow rate was controlled at 0.1mL / h. After spinning, the nanofiber membrane was peeled off from the foam surface and dried in a fume hood for 12 hours to obtain a nanofiber membrane with a two-dimensional honeycomb and three-dimensional spiky dual-coupled microstructure.

[0037] like Figure 3 As shown, Figure 3 The mechanical test diagram of the dual-coupled microstructure nanofiber membrane obtained in Example 3 shows that the maximum tensile strain and stress, as well as the residual strain and residual stress after 100 cycles of stretching, are not as good as those in Example 1, but are better than those of the randomly distributed nanofiber membrane obtained by conventional electrospinning.

[0038] In summary, the two-dimensional honeycomb and three-dimensional spiky dual-coupled microstructure nanofiber membrane prepared by this invention has excellent mechanical properties, with a 77% increase in maximum tensile strain, an 88% increase in maximum tensile stress, and a 27% and 34% reduction in residual strain and residual stress after 100 cycles of tensile testing, respectively.

[0039] The descriptions and practices disclosed in this invention are readily apparent and understandable to those skilled in the art, and various modifications and refinements can be made without departing from the principles of this invention. Therefore, any modifications or improvements made without departing from the spirit of this invention should also be considered within the scope of protection of this invention.

Claims

1. A method for preparing a two-dimensional honeycomb and three-dimensional spinous dual coupling microstructure nanofiber membrane, characterized in that, The method comprises the following steps: Step 1: dissolving the thermoplastic polyurethane (TPU) in an organic solvent, and obtaining a homogeneous spinning solution after heating and stirring; Step 2: performing oxygen plasma treatment on the foam template to make the surface of the foam template present a negative potential; Step 3: injecting the homogeneous spinning solution into a syringe, using the foam as a collector, and performing electrospinning in a high-voltage electrostatic field, controlling the flow rate of the spinning solution by a push pump, peeling the nanofiber membrane from the surface of the foam after the spinning is completed, and drying to obtain a two-dimensional honeycomb and three-dimensional spinous dual-coupling microstructure nanofiber membrane; In the step 1, the organic solvent is selected from any one or more of dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), tetrahydrofuran (THF), dimethylacetamide (DMAc), and N-methyl pyrrolidone (NMP); the mass ratio of the thermoplastic polyurethane and the organic solvent is 1:5-20, the heating temperature is 70-100 DEG C, and the stirring time is 12-24 hours; In the step 2, the foam template is selected from any one of polyurethane foam, polystyrene foam, polyethylene foam, polypropylene foam, silica gel foam, melamine foam, polyether sulfone foam, and polyimide foam; the power of the oxygen plasma treatment is 1000-1500 W, the treatment time is 40-90 seconds, and the surface potential of the foam is-1 kV to-2.5 kV; In the step 3, the voltage of the high-voltage electrostatic field is 15-30 kV, the distance between the foam and the needle tip of the syringe is 15-25 cm, the flow rate of the spinning solution is 0.1-2.5 mL / h, and the drying time is 12-24 hours; The nanofiber membrane has a cross-scale ordered microstructure, including a two-dimensional honeycomb network and a three-dimensional spinous protrusion; the maximum tensile strain of the nanofiber membrane is 200%, the maximum tensile stress is 28.7 MPa, and the residual strain after 100 cycles of tensile stretching is 5.14%.

2. A two-dimensional honeycomb and three-dimensional spinous dual-coupling microstructure nanofiber membrane prepared by the preparation method of claim 1.

3. Use of a two-dimensional honeycomb and three-dimensional spinous dual-coupling microstructure nanofiber membrane prepared by the preparation method of claim 1 in flexible electronic devices, sensors, filtration materials, or biomedical materials.

4. A flexible electronic device, characterized by The two-dimensional honeycomb and three-dimensional spinous dual-coupling microstructure nanofiber membrane of claim 2.

5. A sensor characterized by, The two-dimensional honeycomb and three-dimensional spinous dual-coupling microstructure nanofiber membrane of claim 2.

6. A filter material, characterized by The two-dimensional honeycomb and three-dimensional spinous dual-coupling microstructure nanofiber membrane of claim 2.

7. A biomedical material, characterized by The two-dimensional honeycomb and three-dimensional spinous dual-coupling microstructure nanofiber membrane of claim 2.

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