Electrospinning solutions containing pyridinium propane sulfonate salts and spun films and preparation
By adding propanesulfonic acid pyridine salt to the electrospinning solution, the degree of molecular chain entanglement is improved, which solves the problem of solution jet breakage during electrospinning, and achieves stable fiber formation and cost reduction.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-04-29
- Publication Date
- 2026-06-26
AI Technical Summary
Existing electrospinning solutions cannot form continuous fibers at low viscosity and are difficult to spray at high viscosity, resulting in solution jet breakage and affecting fiber formation.
Adding propanesulfonic acid pyridine salt as an additive to the electrospinning solution improves the degree of entanglement between molecular chains and inhibits solution jet breakage. Using PAN polyacrylonitrile and DMF as the main components, a uniform and dense fiber membrane is formed by stirring and hot rolling.
It effectively suppressed the breakage of the solution jet during electrospinning, improved the microstructure, formed a uniform and dense fiber membrane, and reduced costs.
Smart Images
Figure CN118441360B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to an electrospinning solution and its preparation method, specifically to an electrospinning solution containing pyridine propanesulfonic acid salt, its preparation method, and its electrospinning method. Background Technology
[0002] Electrospinning is the process of spinning a polymer solution under high-voltage static electricity. Electrospinning can produce fibers with diameters ranging from tens to hundreds of nanometers. The products have high porosity and large specific surface area, diverse composition, and uniform diameter distribution, and have high application value in fields such as biomedicine, environmental engineering, and textiles.
[0003] The viscosity of the electrospinning solution plays a crucial role in determining the size and morphology of electrospun fibers. It has been found that at very low solution viscosity, surface tension is the primary controlling factor, resulting in the inability to obtain continuous fibers; only microspheres and beaded fiber structures are formed. When the solution concentration exceeds a critical value, the increased entanglement between molecular chains inhibits the breakage of the solution jet during electrospinning, thus yielding a continuous structure. Within a certain viscosity range, as the solution viscosity increases, the bead shape gradually changes from spherical to spindle-shaped, resulting in increasingly uniform fibers, although the diameter increases. If the solution viscosity increases further, obtaining continuous fibers becomes difficult again, as the high-viscosity solution is difficult to expel from the spinneret to form a continuous jet.
[0004] This invention focuses on modifying electrospinning solutions by adding pyridine propanesulfonic acid salt to the electrospinning solution. This electrospinning solution is inexpensive, improves the entanglement between molecular chains, inhibits the breakage of the solution jet during electrospinning, and improves the microstructure. Summary of the Invention
[0005] This invention provides an electrospinning solution containing propanesulfonic acid pyridinium salt, its preparation method, and its electrospinning method. The electrospinning solution includes additives such as propanesulfonic acid pyridinium salt, PAN polyacrylonitrile, and DMF. The electrospinning solution of this invention is low-cost, improves the entanglement between molecular chains, suppresses the breakage of the solution jet during electrospinning, and improves the microstructure.
[0006] The specific solution adopted in this invention is as follows:
[0007] This invention provides an electrospinning solution containing pyridinium propanesulfonate, comprising:
[0008] Additives, PAN polyacrylonitrile and DMF (N,N-dimethylformamide), the additive being pyridine propane sulfonate (pyridine propane sulfonate).
[0009] In one embodiment, a method for preparing an electrospinning solution containing pyridinium propanesulfonate comprises the following steps:
[0010] Dissolve 1.2-1.6g of PAN polyacrylonitrile in 8-12mL of DMF, and stir for the first time to ensure complete dissolution to obtain a pale yellow solution;
[0011] Pyridinium propanesulfonate was added to the pale yellow solution and stirred a second time to mix it evenly, thus obtaining the electrospinning solution.
[0012] In one embodiment, the molecular weight of PAN is 145,000-155,000, with an optimal value of 148,000-152,000.
[0013] In one embodiment, the concentration of the propanesulfonate pyridine salt additive in the electrospinning solution is 10–50 wt%, preferably 20 wt%.
[0014] In one embodiment, the first stirring time is 10-14 hours, preferably 11-13 hours.
[0015] In one embodiment, the second stirring time is 10.5-13.5 h, with an optimal time of 11.5-12.5 h.
[0016] In one embodiment, it includes:
[0017] The electrospinning solution is injected into the spinning solution storage container;
[0018] The output voltage range of the high-voltage power supply should be selected as 10-14kV, with 11-13kV being optimal.
[0019] Set the distance between the receiving screen and the spinneret to 8-12cm, with 9-11cm being optimal, and begin electrospinning;
[0020] Collect the uniform, dense white initial fiber membrane on the receiving screen;
[0021] The initial fiber membrane is hot-rolled to obtain a spun membrane containing propane sulfonate pyridine salt.
[0022] In one embodiment, it includes:
[0023] The initial fiber membrane thickness is 60–80 μm;
[0024] The thickness of the spun film containing propane sulfonate pyridine salt is 20–30 μm.
[0025] In one embodiment, it includes:
[0026] The hot rolling temperature is 90-110℃, with the optimal temperature being 95-105℃.
[0027] In one embodiment, it includes:
[0028] The temperature for electrospinning is 23-27℃.
[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0030] Adding propanesulfonic acid pyridine salt to the electrospinning solution provides a low-cost solution that improves the entanglement between molecular chains, inhibits the breakage of the solution jet during electrospinning, and enhances the microstructure.
[0031] Test results show that the electrospinning solution of the present invention can effectively suppress the breakage of the solution jet during electrospinning, and the microstructure is improved. Attached Figure Description
[0032] Figure 1 This is a scanning electron microscope image of electrospinning in Embodiment 2 of the present invention.
[0033] Figure 2 This is a scanning electron microscope image of electrospinning in Comparative Example 1 of this invention.
[0034] Figure 3 This is a constant current charge-discharge curve of the zinc / zinc symmetric battery of Embodiment 2 of the present invention under the condition of 0.1 mA cm-2. Detailed Implementation
[0035] This invention provides an electrospinning solution containing propanesulfonic acid pyridinium salt and its preparation method. The electrospinning solution includes additives propanesulfonic acid pyridinium salt, PAN polyacrylonitrile, and DMF. Experimental verification of this invention confirms that the electrospinning solution formed by the additives propanesulfonic acid pyridinium salt, PAN polyacrylonitrile, and DMF under different concentration conditions can improve the degree of entanglement between molecular chains, inhibit the breakage of the solution jet during electrospinning, and improve the microstructure.
[0036] To make the objectives, technical solutions, and advantages of the embodiments and comparative examples of this application clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings of the embodiments and comparative examples of this application.
[0037] Example 1
[0038] This embodiment provides an electrospinning solution containing propane sulfonate pyridine salt and its preparation method. The electrospinning solution includes additives propane sulfonate pyridine salt, PAN polyacrylonitrile and DMF, and the average molecular weight of PAN is 150,000.
[0039] In preparing the electrospinning solution of this embodiment, 1.5 g of PAN polyacrylonitrile was dissolved in 10 mL of LDM at room temperature, and the mixture was stirred for 12 h until it turned pale yellow. Then, pyridinium propanesulfonate was added to a final concentration of 10 wt%, and the mixture was stirred for another 12 h. The homogeneous solution was used as the electrospinning solution. The thorough stirring for both the first and second 12 h effectively improved the entanglement between molecular chains, thereby suppressing the breakage of the solution jet during electrospinning.
[0040] The obtained electrospinning solution was injected into the spinning solution storage container. The spinning temperature was room temperature, the output voltage of the high-voltage power supply was 12 kV, and the distance between the receiving screen and the spinneret was 10 cm. The electrospinning process was stable, and a uniform and dense white fiber film with a thickness of approximately 65 μm was formed on the collecting screen, which was easily peeled off. The spun electrospinned film was hot-rolled at 100°C (pressure 1 MPa) to obtain an electrospinned film containing propanesulfonic acid pyridinium salt with a thickness of approximately 22 μm. The hot-rolling process made the surface of the propanesulfonic acid pyridinium salt-containing electrospinned film smooth, without defects such as breaks or cracks, and the solution jet remained uninterrupted during the electrospinning process.
[0041] Example 2
[0042] This embodiment provides an electrospinning solution containing propane sulfonate pyridine salt and its preparation method. The electrospinning solution includes additives propane sulfonate pyridine salt, PAN polyacrylonitrile and DMF, and the molecular weight of PAN is 150,000.
[0043] In preparing the electrospinning solution of this embodiment, 1.5 g of PAN polyacrylonitrile was dissolved in 10 mL of LDM at room temperature, and the mixture was stirred for 12 h until it turned pale yellow. Then, 20 wt% pyridinium propanesulfonate was added, and the mixture was stirred for another 12 h. The homogeneous solution was used as the electrospinning solution. The thorough stirring for both the first and second 12 h effectively improved the entanglement between molecular chains, thereby suppressing the breakage of the solution jet during electrospinning.
[0044] The obtained electrospinning solution was injected into a self-made spinning solution storage container. The spinning temperature was room temperature, the output voltage of the high-voltage power supply was 12 kV, and the distance between the receiving screen and the spinneret was 10 cm. The electrospinning process was stable, and a uniform and dense white fiber film with a thickness of about 60-80 μm was formed on the collecting screen, which was easily peeled off. The spun electrospinned film was hot-rolled at 100°C to obtain an electrospinned film containing propanesulfonic acid pyridinium salt with a thickness of about 20-30 μm. The hot-rolling process made the surface of the propanesulfonic acid pyridinium salt-containing electrospinned film smooth, without defects such as breaks or cracks, and the solution jet did not interrupt during the electrospinning process.
[0045] Example 3
[0046] This embodiment provides an electrospinning solution containing propane sulfonate pyridine salt and its preparation method. The electrospinning solution includes additives propane sulfonate pyridine salt, PAN polyacrylonitrile and DMF, and the molecular weight of PAN is 150,000.
[0047] In preparing the electrospinning solution of this embodiment, 1.5 g of PAN polyacrylonitrile was dissolved in 10 mL of LDM at room temperature, and the mixture was stirred for 12 h until it turned pale yellow. Then, 30 wt% pyridinium propanesulfonate was added, and the mixture was stirred for another 12 h. The homogeneous solution was used as the electrospinning solution. The thorough stirring for both the first and second 12 h effectively improved the entanglement between molecular chains, thereby suppressing the breakage of the solution jet during electrospinning.
[0048] The obtained electrospinning solution was injected into the spinning solution storage container. The spinning temperature was room temperature, the output voltage of the high-voltage power supply was 12 kV, and the distance between the receiving screen and the spinneret was 10 cm. The electrospinning process was stable, and a uniform and dense white fiber film with a thickness of approximately 60–80 μm was formed on the collecting screen, which was easily peeled off. The spun electrospinned film was hot-rolled at 100°C to obtain an electrospinned film containing propanesulfonic acid pyridinium salt with a thickness of approximately 20–30 μm. The hot-rolling process made the surface of the propanesulfonic acid pyridinium salt-containing electrospinned film smooth, without defects such as breaks or cracks, and the solution jet did not interrupt during the electrospinning process.
[0049] Example 4
[0050] This embodiment provides an electrospinning solution containing propane sulfonate pyridine salt and its preparation method. The electrospinning solution includes additives propane sulfonate pyridine salt, PAN polyacrylonitrile and DMF, and the molecular weight of PAN is 150,000.
[0051] In preparing the electrospinning solution of this embodiment, 1.5 g of PAN polyacrylonitrile was dissolved in 10 mL of LDM at room temperature, and the mixture was stirred for 12 h until it turned pale yellow. Then, 40 wt% pyridinium propanesulfonate was added, and the mixture was stirred for another 12 h. The homogeneous solution was used as the electrospinning solution. The thorough stirring for both the first and second 12 h effectively improved the entanglement between molecular chains, thereby suppressing the breakage of the solution jet during electrospinning.
[0052] The obtained electrospinning solution was injected into the spinning solution storage container. The spinning temperature was room temperature, the output voltage of the high-voltage power supply was 12 kV, and the distance between the receiving screen and the spinneret was 10 cm. The electrospinning process was stable, and a uniform and dense white fiber film with a thickness of approximately 60–80 μm was formed on the collecting screen, which was easily peeled off. The spun electrospinned film was hot-rolled at 100°C to obtain an electrospinned film containing propanesulfonic acid pyridinium salt with a thickness of approximately 20–30 μm. The hot-rolling process made the surface of the propanesulfonic acid pyridinium salt-containing electrospinned film smooth, without defects such as breaks or cracks, and the solution jet did not interrupt during the electrospinning process.
[0053] Example 5
[0054] This embodiment provides an electrospinning solution containing propane sulfonate pyridine salt and its preparation method. The electrospinning solution includes additives propane sulfonate pyridine salt, PAN polyacrylonitrile and DMF, and the molecular weight of PAN is 150,000.
[0055] In preparing the electrospinning solution of this embodiment, 1.5 g of PAN polyacrylonitrile was dissolved in 10 mL of LDM at room temperature, and the mixture was stirred for 12 h until it turned pale yellow. Then, 50 wt% pyridinium propanesulfonate was added, and the mixture was stirred for another 12 h. The homogeneous solution was used as the electrospinning solution. The thorough stirring for both the first and second 12 h effectively improved the entanglement between molecular chains, thereby suppressing the breakage of the solution jet during electrospinning.
[0056] The obtained electrospinning solution was injected into the spinning solution storage container. The spinning temperature was room temperature, the output voltage of the high-voltage power supply was 12 kV, and the distance between the receiving screen and the spinneret was 10 cm. The electrospinning process was stable, and a uniform and dense white fiber film with a thickness of approximately 60–80 μm was formed on the collecting screen, which was easily peeled off. The spun electrospinned film was hot-rolled at 100°C to obtain an electrospinned film containing propanesulfonic acid pyridinium salt with a thickness of approximately 20–30 μm. The hot-rolling process made the surface of the propanesulfonic acid pyridinium salt-containing electrospinned film smooth, without defects such as breaks or cracks, and the solution jet did not interrupt during the electrospinning process.
[0057] Comparative Example 1
[0058] This embodiment provides an electrospinning solution and its preparation method. The electrospinning solution includes PAN polyacrylonitrile and DMF, and the molecular weight of PAN is 150,000.
[0059] In preparing the electrospinning solution of this embodiment, 1.5 g of PAN polyacrylonitrile was dissolved in 10 mL of LDM at room temperature and stirred for 12 h until it turned pale yellow. The well-mixed solution was then used as the electrospinning solution.
[0060] The obtained electrospinning solution was injected into the spinning solution storage container. The spinning temperature was room temperature, the output voltage of the high-voltage power supply was 12 kV, and the distance between the receiving screen and the spinneret was 10 cm. During the electrospinning process, a white fiber film with a thickness of approximately 60–80 μm was formed on the collecting screen. The spun electrospinned film was then hot-rolled at 100 °C to obtain an electrospinned membrane with a thickness of approximately 20–30 μm.
[0061] A 0.1 mm thick zinc sheet was used as the negative electrode and a 0.1 mm thick zinc sheet was used as the positive electrode. A 2 M zinc sulfate solution was used as the electrolyte. An electrospun membrane prepared in Example 2 was used as the separator to assemble a button-type zinc / zinc symmetric battery.
[0062] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for preparing an electrospinning solution containing pyridinium propanesulfonate, characterized in that: The electrospinning solution comprises: Additives, PAN polyacrylonitrile and DMF, wherein the additive is pyridinium propane sulfonate; 1.2-1.6 g of PAN polyacrylonitrile is dissolved in 8-12 mL of DMF, and the concentration of the propane sulfonate pyridinium salt additive in the electrospinning solution is 18-22 wt%. The molecular weight of the PAN is 145,000-155,000. The specific steps for preparing the electrospinning solution containing propane sulfonate pyridinium salt are as follows: Dissolve 1.2-1.6 g of the PAN polyacrylonitrile in 8-12 mL of the DMF, and stir for the first time to ensure complete dissolution to obtain a pale yellow solution; The propane sulfonate pyridinium salt is added to the pale yellow solution, and the mixture is stirred a second time to make it homogeneous, thus obtaining an electrospinning solution; The first stirring time is 10-14 hours, and the second stirring time is 10.5-13.5 hours.
2. The preparation method according to claim 1, characterized in that: 1.4-1.6g of PAN (polyacrylonitrile) is dissolved in 8-12mL of DMF, wherein the molecular weight of PAN is 148,000-152,000. The first stirring time is 11-13 hours; The second stirring time is 11.5-12.5 hours.
3. An electrospinning solution containing propanesulfonic acid pyridine salt prepared by the method for preparing an electrospinning solution containing propanesulfonic acid pyridine salt as described in claim 1 or 2.
4. A method for electrospinning a film using the electrospinning solution containing propanesulfonic acid pyridinium salt as described in claim 3, characterized in that: include: The electrospinning solution described in claim 3 is injected into the spinning solution storage chamber of the electrospinning equipment; Select an output voltage level of 10-14kV for the high-voltage power supply. Set the distance between the receiving screen and the spinneret to 8-12cm and start electrostatic spinning; Collect the uniform and dense initial fiber membrane on the receiving screen; The initial fiber membrane is hot-rolled to obtain a spun membrane containing pyridine propane sulfonate.
5. The method according to claim 4, characterized in that: include: The electrospinning solution described in claim 3 is injected into the spinning solution storage chamber of the electrospinning equipment; Select an output voltage level of 11-13kV for the high-voltage power supply; Set the distance between the receiving screen and the spinneret to 9-11cm and begin electrostatic spinning; Collect the uniform and dense initial fiber membrane on the receiving screen; The initial fiber membrane is hot-rolled to obtain a spun membrane containing pyridine propane sulfonate.
6. The method according to claim 4, characterized in that: include: The initial fiber membrane thickness is 60~80μm; The thickness of the spun film containing propane sulfonate pyridine salt is 20~30μm; The hot rolling temperature is 90-110℃. The electrospinning temperature is 23-27℃.
7. The method according to claim 4, characterized in that: include: The hot rolling temperature is 95-105℃.
8. A spun membrane prepared by electrospinning a pyridinium propane sulfonate electrospinning solution as described in any one of claims 4-7.