CN109860485B - Polyimide nanofiber diaphragm and manufacturing method thereof - Google Patents
Polyimide nanofiber diaphragm and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a polyimide nanofiber membrane and a manufacturing method thereof, which are characterized by comprising the following steps: s1, preparing a modifier, S2, preparing a spinning solution, S3, preparing an electrostatic spinning diaphragm, S4, preparing a nanofiber diaphragm, S5 and preparing a polyimide diaphragm. The invention uses a method of adding a self-made modifier and polyamide acid for co-spinning, thereby achieving the purposes of greatly improving the strength of the nanofiber diaphragm and reducing the aperture of the nanofiber diaphragm; the method of the invention also has the following technical effects: the mechanical property of the polyimide nanofiber membrane is remarkably improved, the applicable polyimide resin has a wide structure, and the heat resistance of the polyimide resin can be improved; the modifier can form good connection with the polyimide fiber through a surface chemical structure and self fusion deformation in the preparation process, and the stability and the mechanical property of the fiber diaphragm are improved.
Description
Technical Field
The invention relates to a method for preparing a polyimide nanofiber diaphragm by an electrostatic spinning method, in particular to a polyimide nanofiber diaphragm with high strength, high temperature resistance and high puncture strength and a preparation method thereof.
Background
Polyimide is a cyclic chain compound with a molecular structure containing an imide structure, and has excellent performances of high strength, high modulus, high temperature resistance, low temperature resistance, radiation resistance and the like, excellent solvent resistance and dimensional stability, and good biocompatibility and dielectric property. The polyimide nanofiber membrane prepared by the electrostatic spinning method is a material which attracts attention at present because of the combination of the characteristics of large specific surface area, high porosity, high temperature resistance and chemical stability of polyimide of the fiber membrane. At present, due to the disordered arrangement and fluffy volume of superfine fibers, the polyimide nanofiber membrane prepared by the existing electrostatic spinning method has the defects that the fibers are simply physically stacked and do not have strong interaction, so that the mechanical property of the nanofiber membrane is usually poor, the pore diameter is large, and the practical application of the nanofiber membrane is greatly limited. Firstly, the strength of the nanofiber membrane is improved through physical or chemical crosslinking, for example, a polyimide fiber membrane with a crosslinked structure is prepared through a method of heat treatment after polyamide acid fiber membrane is treated by alkali liquor, but the method needs the processes of alkali liquor treatment and water washing, and the process is slightly complex; or the hot-melt resin and the polyimide resin are co-spun, and the hot-melt resin can be melted at high temperature and subjected to melting micro-crosslinking through heat treatment. The other method is to coat ceramic slurry on the surface to improve the strength of the nanofiber membrane and reduce the aperture, but the method has limited improvement on the strength of the polyimide nanofiber membrane, and the adhesion between ceramic particles and the membrane is poor, so that the phenomenon of powder falling is easily caused, and the durability is poor.
Disclosure of Invention
Aiming at the defects of low tensile strength, low puncture resistance strength and overlarge pore diameter of the polyimide nanofiber membrane prepared by an electrostatic spinning method in the prior art, the invention provides the polyimide nanofiber membrane which has the characteristics of simple process, wide application range, high strength, good temperature resistance, high puncture resistance strength, high porosity, small pore diameter and the like, and the preparation method thereof.
In order to realize the technical purpose, the invention provides a preparation method of a polyimide nanofiber membrane, which comprises the following steps:
s1, preparing a modifier, and modifying the surface of the glass powder to prepare the modifier;
s2, preparing spinning solution, and blending a modifier and a polyamide acid (PAA) solution to prepare the spinning solution;
s3, preparing an electrostatic spinning diaphragm, and preparing a (loose) electrostatic spinning diaphragm from the spinning solution through electrostatic spinning;
s4, preparing a nanofiber membrane, and preparing the (loose) electrostatic spinning membrane into the nanofiber membrane through hot pressing;
and S5, preparing a polyimide diaphragm, and carrying out segmented heat treatment on the nanofiber diaphragm to obtain the polyimide diaphragm.
Preferably, the glass frit is a low melting point glass frit.
Preferably, the melting temperature of the low-melting-point glass powder is 300-500 ℃, and the granularity is 100-2000 meshes.
Specifically, the modifying method for modifying the surface of the glass powder into the modifying agent comprises the following steps: adding the glass powder into a coupling agent solution containing 5-50 wt%, stirring at the temperature of 5-80 ℃ at the rotating speed of 100-8000 r/min for 0.5-10 h, filtering and drying to obtain the modifier.
Preferably, the coupling agent is selected from one or more of silane coupling agents containing amino, vinyl, epoxy, acrylate and acryloxy groups, and the solvent used in the coupling agent solution is selected from: one or more of water, ethanol, methanol, acetone, N-propanol, isopropanol, ethylene glycol, propylene glycol, N '-dimethylformamide, N' -dimethylacetamide and dimethylsulfoxide.
Specifically, the preparation method of the modifying agent and polyamic acid (PAA) blending solution comprises the following steps: stirring at-5 deg.C-20 deg.C for 0.5h-2h to obtain spinning solution, wherein the weight ratio of modifier and polyamic acid (PAA) is (1: 20) - (1: 1), preferably (1: 20) - (1: 10). The weight ratio of the modifier to the polyamic acid is 1: 20 to 1: 1, the performance of the diaphragm is affected by too large addition amount, and the addition amount is too small to play a corresponding role.
Preferably, the concentration of the polyamic acid (PAA) solution is 5 wt% to 18 wt%, and the solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, methanol, ethanol and isopropanol.
Specifically, the electrostatic spinning process conditions comprise that the spinning flow is 0.01mL/min-1mL/min, the distance from the needle point to a receiving plate or a receiving roller is 100mm-500mm, and the spinning voltage is 10KV-30 KV.
Specifically, the hot pressing process conditions comprise a hot pressing temperature of 100-150 ℃, a hot pressing pressure of 10-30 KG and a hot pressing time: 0.1s-2 s.
Specifically, the step of obtaining the polyimide diaphragm by the segmented heat treatment comprises a first stage: the heating rate is 1 ℃/min-10 ℃/min, the final heat treatment temperature of the stage is 80-120 ℃, the temperature is raised to the heat treatment temperature, and the temperature is kept for 30 min; and a second stage: the heating rate is 1 ℃/min-10 ℃/min, the final heat treatment temperature is 220 ℃ to 450 ℃, the temperature is raised to the heat treatment temperature, and the temperature is kept for 30min-60 min.
Another object of the present invention is to provide a polyimide nanofiber membrane comprising polyimide and a low melting point glass frit.
Further, the melting temperature of the low-melting-point glass powder is 300-500 ℃.
Further, the polyimide nano-film is prepared by the method.
The technical scheme of the invention has the following advantages:
the method of adding a self-made modifier and polyamide acid for co-spinning is used, so that the purposes of greatly improving the strength of the nanofiber membrane and reducing the aperture of the nanofiber membrane are achieved;
compared with the prior art, the method of the invention also has the following technical effects:
1. the polyimide nanofiber membrane prepared by the method has a physical cross-linking structure, and the introduction of cross-linking points remarkably improves the mechanical property of the polyimide nanofiber membrane;
2. compared with the conventional organic resin blending modified polyimide nanofiber diaphragm method, the method provided by the invention is applicable to a wide range of polyimide resin structures, and can improve the heat resistance of the polyimide resin;
3. compared with the conventional method for modifying the polyimide nanofiber membrane by inorganic/polyimide blending, the modifier disclosed by the invention can form good connection with polyimide fibers through a surface chemical structure and self fusion deformation in the preparation process, so that the stability and the mechanical property of the fiber membrane are improved.
4. The preparation method has simple process route, and the prepared polyimide nanofiber membrane has excellent performance and better industrialization prospect.
Detailed Description
The present invention is described below based on examples, and it should be understood by those of ordinary skill in the art that the embodiments provided herein are for illustrative purposes, and the scope of the present invention is not limited to the following examples.
For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
A preparation method of a polyimide nanofiber membrane comprises the following specific steps:
s1 preparation of modifier
Adding glass powder with the melting point of 350 ℃ and the granularity of 1000 meshes into 10 wt% of ethanol solution of 3-aminopropyl triethoxysilane, stirring for 2 hours at the rotating speed of 2000r/min at the temperature of 30 ℃, and then filtering and drying to obtain a modifier;
s2 preparation of spinning solution
Adding the modifier into a polyamide acid (PAA) solution prepared by taking 4,4' -diphenyl ether dianhydride (ODPA) and 4, 4-diphenyl ether diamine (ODA) as raw materials, and stirring for 0.5h at the temperature of 0 ℃ to prepare the spinning solution. The weight ratio of the modifier to the PAA is 1: 20; concentration of PAA solution: a 10 wt% solution; the solvent is as follows: n, N' -dimethylformamide;
S3, preparing the electrostatic spinning diaphragm
Preparing the spinning solution prepared in the step S2 into a loose electrostatic spinning diaphragm by adopting an electrostatic spinning method, wherein the electrostatic spinning process conditions are as follows: the spinning flow rate is as follows: 0.5mL/min, the distance from the needle point to the receiving plate or the receiving roller is 300mm, and the spinning voltage is as follows: 25 KV;
s4 preparation of nanofiber membrane
And (4) carrying out a hot-pressing processing process on the electrostatic spinning diaphragm prepared in the step S3 to obtain a nanofiber diaphragm, wherein the hot-pressing process conditions are as follows: hot pressing temperature: the hot pressing pressure is as follows at 110 ℃: 25KG, hot pressing time: 0.5 s;
s5 preparation of polyimide diaphragm
Placing the nanofiber membrane prepared in the step S4 in a high-temperature oven, and preparing a polyimide membrane by adopting a segmented heat treatment method, wherein in the first stage: the heating rate is as follows: heating to 80 ℃ at the temperature of 5 ℃/min, keeping for 30min, and in the second stage: the heating rate is as follows: 5 ℃/min, final heat treatment temperature: keeping the temperature at 350 ℃ for 60 min.
Example 2
S1 preparation of modifier
Adding glass powder with the melting point of 400 ℃ and the granularity of 1200 meshes into an ethanol/water (95v/5v) solution of 12 wt% of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, stirring for 4h at the rotating speed of 5000r/min at the temperature of 25 ℃, and then filtering and drying to obtain a modifier;
S2, preparing spinning solution
Adding the modifier into a polyamic acid (PAA) solution prepared by taking pyromellitic dianhydride (PMDA) and 4, 4-diphenyl ether diamine (ODA) as raw materials, and stirring for 1h at the temperature of 5 ℃ to prepare a spinning solution. The weight ratio of the modifier to the PAA is as follows: 1: 15. concentration of PAA solution: a 12 wt% solution; the solvent is as follows: n, N' -dimethylformamide/tetrahydrofuran (80v/20 v);
s3 preparation of electrostatic spinning diaphragm
Preparing the spinning solution prepared in the step S2 into a loose electrostatic spinning diaphragm by adopting an electrostatic spinning method, wherein the electrostatic spinning process conditions are as follows: the spinning flow rate is as follows: 0.3mL/min, the distance from the needle point to the receiving plate or the receiving roller is 300mm, and the spinning voltage is as follows: 25 KV;
s4 preparation of nanofiber membrane
And (4) carrying out a hot-pressing processing process on the electrostatic spinning diaphragm prepared in the step S3 to obtain a nanofiber diaphragm, wherein the hot-pressing process conditions are as follows: hot pressing temperature: the hot pressing pressure is as follows at 110 ℃: 25KG, hot pressing time: 1 s;
s5 preparation of polyimide diaphragm
Placing the nanofiber membrane prepared in the step S4 in a high-temperature oven, and preparing a polyimide membrane by adopting a segmented heat treatment method, wherein in the first stage: the heating rate is as follows: heating to 80 ℃ at the temperature of 5 ℃/min, keeping for 30min, and in the second stage: the heating rate is as follows: 5 ℃/min, final heat treatment temperature: keeping at 400 deg.C for 45 min.
Example 3
S1 preparation of modifier
Adding glass powder with melting point of 450 ℃ and particle size of 2000 meshes into 12 wt% of ethanol/n-propanol (60v/40v) solution of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring for 4h at the temperature of 50 ℃ and the rotating speed of 8000r/min, and then filtering and drying to obtain the modifier.
S2 preparation of spinning solution
The modifier is added into a polyamic acid (PAA) solution prepared by taking 4,4 '-diphenyl ether dianhydride (ODPA) and 2,2' -bis (trifluoromethoxy) -biphenyl diamine as raw materials, and the solution is stirred for 2 hours at the temperature of 0 ℃ to prepare spinning solution. The weight ratio of the modifier to the PAA is as follows: 1: 12. concentration of PAA solution: 8 wt% solution; the solvent is as follows: n-methylpyrrolidone/ethanol (90v/10 v).
S3 preparation of electrostatic spinning diaphragm
Preparing the spinning solution prepared in the step S2 into a loose electrostatic spinning diaphragm by adopting an electrostatic spinning method, wherein the electrostatic spinning process conditions are as follows: the spinning flow rate is as follows: 0.1mL/min, the distance from the needle point to the receiving plate or the receiving roller is 250mm, and the spinning voltage is as follows: 30 KV;
s4 preparation of nanofiber membrane
And (4) carrying out a hot-pressing processing process on the electrostatic spinning diaphragm prepared in the step S3 to obtain a nanofiber diaphragm, wherein the hot-pressing process conditions are as follows: hot pressing temperature: the hot pressing pressure is as follows at 110 ℃: 25KG, hot pressing time: 1 s;
S5 preparation of polyimide diaphragm
Placing the nanofiber membrane prepared in the step S4 in a high-temperature oven, and preparing a polyimide membrane by adopting a segmented heat treatment method, wherein in the first stage: the heating rate is as follows: heating to 100 ℃ at the temperature of 5 ℃/min, keeping for 30min, and in the second stage: rate of temperature rise: 5 ℃/min, final heat treatment temperature: keeping the temperature at 450 ℃ for 40 min.
Comparative example:
s1 preparation of electrostatic spinning diaphragm
Preparing a loose electrostatic spinning diaphragm from a polyamic acid (PAA) solution prepared by taking 4,4' -diphenyl ether dianhydride (ODPA) and 4, 4-diphenyl ether diamine (ODA) as raw materials by an electrostatic spinning method, wherein: concentration of PAA solution: a 16 wt% solution; the solvent is as follows: n, N' -dimethylacetamide. The electrostatic spinning process conditions are as follows: the spinning flow rate is as follows: 0.1mL/min, the distance from the needle point to the receiving plate or the receiving roller is 300mm, and the spinning voltage is as follows: 20 KV;
s2 preparation of nanofiber membrane
And (4) carrying out a hot-pressing processing process on the electrostatic spinning diaphragm prepared in the step S1 to obtain a nanofiber diaphragm, wherein the hot-pressing process conditions are as follows: hot pressing temperature: the hot pressing pressure is as follows at 105 ℃: 20KG, hot pressing time: 0.3 s;
s3 preparation of polyimide diaphragm
Placing the nanofiber membrane prepared in the step S2 in a high-temperature oven, and preparing a polyimide membrane by adopting a segmented heat treatment method, wherein in the first stage: the heating rate is as follows: heating to 80 ℃ at the temperature of 5 ℃/min, keeping for 30min, and in the second stage: the heating rate is as follows: 5 ℃/min, final heat treatment temperature: and (3) raising the temperature to the heat treatment temperature at 300 ℃, and keeping the temperature for 20 min.
Compared with a pure polyimide nanofiber membrane prepared by an electrostatic spinning method, the invention adds a modifier prepared by modifying the surface of self-made low-melting-point glass powder, and the modified polyimide nanofiber membrane prepared by using the modifier and a polyamic acid co-spinning method has the characteristics of simple process, wide application range, high strength, good temperature resistance, high puncture strength, high porosity, small aperture and the like under the control of strict process parameters and conditions, thereby being beneficial to solving the safety and service life of a power battery and widening the application field of the polyimide nanofiber membrane. Specific properties are compared in table 1 below.
Table 1 comparison of polyimide nanofiber membranes
Claims (7)
1. A preparation method of a polyimide nanofiber membrane is characterized by comprising the following steps:
s1, preparing a modifier, and modifying the surface of the glass powder to prepare the modifier;
s2, preparing spinning solution, and blending a modifier and a polyamide acid PAA solution to prepare the spinning solution;
s3, preparing an electrostatic spinning diaphragm, and preparing the spinning solution into the electrostatic spinning diaphragm through electrostatic spinning;
s4, preparing a nanofiber membrane, and preparing the nanofiber membrane from the electrostatic spinning membrane through hot pressing;
S5, preparing a polyimide diaphragm, and carrying out segmented heat treatment on the nanofiber diaphragm to obtain the polyimide diaphragm;
the melting temperature of the glass powder is 300-500 ℃, and the granularity is 100-2000 meshes;
the modification method for modifying the surface of the glass powder into the modifier comprises the following steps: adding glass powder into a coupling agent solution containing 5-50 wt%, stirring at the temperature of 5-80 ℃ for 0.5-10 h at the rotating speed of 100-8000 r/min, filtering and drying to obtain the modifier.
2. The preparation method according to claim 1, wherein the coupling agent is selected from one or more of silane coupling agents containing amino group, vinyl group, epoxy group, acrylate group and acryloxy group, and the solvent used in the coupling agent solution is selected from: one or more of water, ethanol, methanol, acetone, N-propanol, isopropanol, ethylene glycol, propylene glycol, N '-dimethylformamide, N' -dimethylacetamide and dimethylsulfoxide.
3. The preparation method of claim 1, wherein the preparation method of the modifier and polyamic acid PAA blending solution comprises: stirring for 0.5h-2h at the temperature of-5 ℃ to 20 ℃ to prepare a spinning solution, wherein the weight ratio of the modifier to the polyamide acid PAA is (1: 20) - (1: 1).
4. The method according to claim 1, wherein the concentration of the polyamic acid PAA solution is 5 wt% to 18 wt%, and the solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, methanol, ethanol, and isopropanol.
5. The preparation method according to claim 1, wherein the electrostatic spinning process conditions are a spinning flow rate of 0.01mL/min to 1mL/min, a distance from a needle point to a receiving plate or a receiving roller of 100mm to 500mm, and a spinning voltage of 10KV to 30 KV.
6. The preparation method according to claim 1, wherein the hot pressing process conditions are a hot pressing temperature of 100 ℃ to 150 ℃, a hot pressing pressure of 10KG to 30KG, a hot pressing time: 0.1s-2 s; the specific steps of obtaining the polyimide diaphragm by adopting the segmented heat treatment comprise a first stage: the heating rate is 1 ℃/min-10 ℃/min, the final heat treatment temperature of the stage is 80-120 ℃, the temperature is raised to the heat treatment temperature, and the temperature is kept for 30 min; and a second stage: the heating rate is 1 ℃/min-10 ℃/min, the final heat treatment temperature is 220 ℃ to 450 ℃, the temperature is raised to the heat treatment temperature, and the temperature is kept for 30min-60 min.
7. A polyimide nanofiber membrane characterized by being prepared by the method as set forth in any one of claims 1 to 6.
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| CN111640902A (en) * | 2020-06-08 | 2020-09-08 | 淮北市吉耐新材料科技有限公司 | Preparation process of lithium battery diaphragm |
| CN113604014A (en) * | 2021-08-24 | 2021-11-05 | 江阴市宏丰塑业有限公司 | High-weather-resistance high-rigidity glass fiber reinforced PBT (polybutylene terephthalate) -PET (polyethylene terephthalate) alloy modified material |
| CN114635230B (en) * | 2022-04-02 | 2024-03-26 | 天津工业大学 | Bulk super-hydrophobic nanofiber membrane for membrane distillation and preparation method thereof |
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