CN111705429A - High-molecular nano-fiber film and preparation method thereof - Google Patents
High-molecular nano-fiber film and preparation method thereof Download PDFInfo
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- CN111705429A CN111705429A CN202010425809.4A CN202010425809A CN111705429A CN 111705429 A CN111705429 A CN 111705429A CN 202010425809 A CN202010425809 A CN 202010425809A CN 111705429 A CN111705429 A CN 111705429A
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- D01D5/0007—Electro-spinning
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
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Abstract
The invention discloses a polymer nanofiber membrane and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving an insulating high molecular polymer in a solvent, and performing molecular chain unwrapping treatment in the dissolving process to prepare spinning solution; adopting spinning solution to carry out electrostatic spinning, and adopting parallel electrodes to collect the high-molecular nano-fibers to prepare a crude product of the high-molecular nano-fiber film; and (3) carrying out hot stretching on the crude product of the polymer nanofiber membrane. Through the mode, the synergetic and ordered arrangement of molecular chains and fibers in the polymer nanofiber membrane can be realized, and the heat-conducting property of the polymer nanofiber membrane material is greatly improved.
Description
Technical Field
The invention relates to the technical field of heat-conducting high polymer materials, in particular to a high polymer nanofiber film and a preparation method thereof.
Background
With the increasing degree of miniaturization and integration of modern devices, the heat flux density of the devices is gradually increased, which leads to the increase of the working temperature of the devices, and researches show that the reliability and the service life of the devices mainly depend on the working temperature, and the performance and the service life of the devices are rapidly reduced due to the slight increase of the temperature, so that the fact that the heat of the devices can be rapidly transferred out becomes the key for ensuring the stable work of the devices is critical to the modern heat management technology, the heat management technology becomes the common key technology in the fields of modern microelectronic development, communication technology, new energy automobiles and the like, and the high-efficiency thermal interface material is one of the main bottlenecks of the heat management technology.
Although traditional heat dissipation materials such as metal, carbon materials and the like have high heat conduction performance, the traditional heat dissipation materials also have the problem of electric conduction; although nitrides, metal oxides and other inorganic non-metallic materials are insulating, the defects of high specific gravity or brittleness exist, and the application of the traditional heat dissipation materials in the field of heat dissipation is limited. At present, researchers mainly focus on polymer heat dissipation materials, but at present, the heat conductivity of polymer materials is low, high heat conduction characteristics are obtained mainly by adding high heat conduction fillers such as carbon fiber core materials and inorganic oxides, and the prepared composite thermal interface materials are widely used in the field of electronic heat dissipation, such as heat conduction gaskets, heat conduction silicone grease, heat conduction paste and the like. However, the thermal conductivity of the current thermal interface materials is mostly less than 10W/(m.K), and the heat dissipation requirements of highly integrated devices are difficult to meet. One of the main reasons for the low thermal conductivity of the thermal interface material is the poor performance of the high thermal conductive filler. Therefore, how to prepare the high thermal conductive polymer material by avoiding the bottleneck of the thermal conductive filler becomes a problem to be solved urgently.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the polymer nanofiber membrane and the preparation method thereof, which can realize the cooperative ordered arrangement of molecular chains and fibers in the polymer nanofiber membrane and improve the heat-conducting property of a polymer nanofiber membrane material.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, a method for preparing a polymer nanofiber membrane is provided, which comprises the following steps:
s1, dissolving the insulating high molecular polymer in a solvent, and performing molecular chain unwrapping treatment in the dissolving process to prepare spinning solution;
s2, performing electrostatic spinning by using the spinning solution, and collecting the polymer nanofibers by using parallel electrodes to prepare a crude product of the polymer nanofiber membrane;
s3, carrying out hot stretching on the crude product of the polymer nanofiber membrane.
According to some embodiments of the invention, in step S1, the molecular chain unwrapping process is an external force assisted unwrapping process.
According to some embodiments of the invention, the external force assisted unwrapping process is selected from at least one of an ultrasonic process, an oscillating process, a vibrating process, a shearing process, a stirring process.
According to some embodiments of the invention, in step S1, the mass ratio of the insulating high molecular polymer to the solvent is 1: (1-50).
According to some embodiments of the invention, the insulating high molecular polymer is selected from at least one of polyethylene, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile, and polyvinylidene fluoride.
According to some embodiments of the invention, the solvent is selected from at least one of water, diethyltriamine, triethyltetramine and dimethylsulfoxide.
According to some embodiments of the invention, in the step S1, the dissolving temperature of the dissolving process is 30-100 ℃.
According to some embodiments of the invention, in the step S3, the hot stretching temperature is 70 to 200 ℃. The stretching ratio is generally 2 to 15.
According to some embodiments of the present invention, in step S2, a fiber orientation degree detection device is used to detect the orientation degree of the polymer nanofiber in real time, so as to adjust the parameter of electrostatic spinning in real time according to the detected orientation degree of the polymer nanofiber, thereby achieving the adjustment and control of the orientation degree of the polymer nanofiber. The fiber orientation degree detection device can specifically adopt a laser diffraction device.
In a second aspect of the present invention, a polymer nanofiber membrane is provided, which is prepared by any one of the methods for preparing a polymer nanofiber membrane provided in the first aspect of the present invention.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a preparation method of a high-molecular nanofiber membrane, which is based on a material design idea of two-stage structure order, wherein the two stages comprise ordered arrangement of insulating high-molecular polymer molecular chains along the axial direction of fibers and consistent orientation of fibers in the nanofiber membrane, and the heat-conducting property of the membrane material can be improved to the greatest extent. The method specifically comprises the steps of taking a macromolecular solution obtained through molecular chain unwrapping treatment as a spinning solution, preparing through electrostatic spinning, collecting with parallel electrodes to obtain a macromolecular nano-fiber film crude product, and then carrying out hot stretching on the macromolecular nano-fiber film crude product. In the preparation process of the spinning solution, the molecular chain unwinding treatment is beneficial to improving the molecular chain orientation degree and improving the crystallinity of a high polymer; in the electrostatic spinning process, molecular chains can be oriented along the axial direction of the fiber under the stretching action of electrostatic force; in addition, the parallel electrodes are used as a receiving device to receive the polymer nano-fibers, and the special electric field distributed between the parallel electrodes can enable the two ends of the fibers to be acted by the electric field force in the direction vertical to the axis of the electrodes, and the electric field force enables the fibers to be uniformly and parallelly arranged in the direction vertical to the axial direction of the parallel electrodes; and finally, carrying out hot stretching on the crude product of the polymer nanofiber membrane, so that molecular chains can be further oriented along the axial direction of the fiber, and the crystallinity of the polymer can be improved, thereby realizing the cross-scale ordered arrangement and assembly of the molecular chains and the two-stage structure of the fiber, and obtaining the polymer nanofiber membrane with high heat conductivity.
Drawings
FIG. 1(a) is a schematic view of electrospinning in a method for preparing a polymer nanofiber membrane according to example 1;
FIG. 1(b) is a schematic diagram of the electric field distribution between parallel electrodes in FIG. 1 (a);
FIG. 1(c) is a diagram of the polymer nanofibers on parallel electrodes in the electrospinning process shown in FIG. 1 (a);
FIG. 2 is a wide-angle X-ray scattering spectrum of the polymer nanofiber thin film prepared in examples 1-4;
FIG. 3 is a wide-angle X-ray scattering spectrum of the polymer nanofiber thin film prepared in examples 5 to 7;
FIG. 4 is a wide-angle X-ray scattering spectrum of the polymer nanofiber thin films prepared in comparative examples 1 to 3;
fig. 5 is SEM images of the polymer nanofiber thin films prepared in comparative example 1 and comparative example 2.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
A preparation method of a polymer nanofiber membrane comprises the following steps:
s1, weighing 1 part by weight of polyvinyl alcohol and 10 parts by weight of water, mixing and uniformly stirring, and then performing high-power ultrasonic treatment at 800W for half an hour to perform molecular chain unwinding treatment to prepare a spinning solution;
s2, performing electrostatic spinning by using the spinning solution prepared in the step S1, and collecting the polymer nanofibers by using a self-made parallel electrode; the parallel electrode is composed of two metal flat plates which are placed in parallel; the nozzle direction of a material cylinder containing spinning solution is vertical to the long axis direction of the electrode, nano fibers sprayed out from the nozzle are lapped between two metal flat plates and are uniformly arranged along the long axis direction vertical to the metal flat plates, and then the nano fibers are superposed layer by layer to form a crude product of the polymer nano fiber film; during preparation, a self-built laser diffraction device is adopted to detect the orientation degree of the polymer nanofiber in real time, and parameters of electrostatic spinning are adjusted in real time according to the detected orientation degree of the polymer nanofiber, so that high-orientation preparation of the polymer nanofiber is realized;
s3, heating the crude product of the polymer nanofiber membrane prepared in the step S2, and stretching the crude product 2 times at 150 ℃ to finally obtain the polymer nanofiber membrane with high heat conductivity.
As shown in fig. 1(a), electrospinning was performed in the above embodiment using the parallel electrodes 3 as collecting means. Specifically, the spinning solution is injected into the cylinder 2, a positive voltage is applied to the cylinder 2 through the high-voltage power supply 1, a negative voltage is applied to the parallel electrode 3, the spinning solution in the cylinder 2 ejects the polymer nanofibers 4 from the nozzle of the cylinder 2 under the action of the voltage, an electric field between the nozzle and the parallel electrode 3 pulls the polymer nanofibers 4 to move towards the parallel electrode 3, the electric field distribution between the parallel electrodes 3 is shown in fig. 1(b), and the electric field between two metal flat plates of the parallel electrode 3 enables the polymer nanofibers 4 to be arranged in parallel along the axial direction perpendicular to the parallel electrode 3. The force of the polymer nanofibers 4 on the parallel electrodes 3 is specifically shown in fig. 1(c), where F is an electrostatic force. In addition, in the above embodiment, the macromolecular chains are unwound under the action of high-power ultrasound, and are axially arranged along the fiber under the action of an electric field force along the axial direction of the fiber in the electrostatic spinning process, so as to realize a film consisting of orderly arranged molecular chains and nanofibers; the arrangement condition of the fibers is observed in real time by adopting the built laser diffraction device, so that the adjustment and optimization of electrostatic spinning conditions are facilitated, and the high-orientation fibers are obtained; combining the above treatments, and then stretching the nanofiber film with two-stage ordered arrangement at 150 ℃, wherein the stretching ratio is 2 times, and finally obtaining the high-molecular nanofiber film with high thermal conductivity.
Example 2
A preparation method of a polymer nanofiber membrane comprises the following steps:
s1, weighing 1 part by weight of polyvinyl alcohol and 10 parts by weight of water, mixing and uniformly stirring, and then carrying out high-power ultrasonic treatment for half an hour at 800W to prepare a spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by adopting a self-made parallel electrode; the parallel electrode is composed of two metal flat plates which are placed in parallel, the nozzle direction of a material cylinder for containing spinning solution is vertical to the long axis direction of the electrode, the polymer nano-fibers sprayed out by the nozzle are lapped between the two metal flat plates and are uniformly arranged along the long axis direction vertical to the metal flat plates, and then the polymer nano-fibers are overlapped layer by layer to form a crude polymer nano-fiber film; during preparation, a laser diffraction device built by the user is adopted to detect the orientation degree of the polymer nanofiber in real time, and parameters of electrostatic spinning are adjusted in real time according to the detected orientation degree of the polymer nanofiber so as to realize high-orientation preparation of the polymer nanofiber;
s3, heating the crude product of the polymer nanofiber membrane prepared in the step S2, and stretching the crude product 6 times at 150 ℃ to obtain the polymer nanofiber membrane.
Example 3
A preparation method of a polymer nanofiber membrane comprises the following steps:
s1, weighing 1 part by weight of polyvinyl alcohol and 10 parts by weight of water, mixing and uniformly stirring, and then carrying out high-power ultrasonic treatment for half an hour at 800W to prepare a spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by adopting a self-made parallel electrode; the parallel electrode is composed of two metal flat plates which are placed in parallel, the nozzle direction of a material cylinder for containing spinning solution is vertical to the long axis direction of the electrode, the nano-fibers sprayed out by the nozzle are lapped between the two metal flat plates and are uniformly arranged along the long axis direction vertical to the metal flat plates, and then the nano-fibers are overlapped layer by layer to form a crude product of the polymer nano-fiber film; during preparation, a laser diffraction device built by the user is adopted to detect the orientation degree of the polymer nanofibers in real time, and parameters of electrostatic spinning are adjusted in real time according to the detected orientation degree of the polymer nanofibers, so that high-orientation preparation of the polymer nanofibers is realized;
s3, heating the crude product of the polymer nanofiber membrane prepared in the step S2, and stretching the crude product 9 times at 150 ℃ to obtain the polymer nanofiber membrane.
Example 4
A preparation method of a polymer nanofiber membrane comprises the following steps:
s1, weighing 1 part by weight of polyvinyl alcohol and 10 parts by weight of water, mixing and uniformly stirring, and then carrying out high-power ultrasonic treatment for half an hour at 800W to prepare a spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by adopting a self-made parallel electrode; the parallel electrode is composed of two metal flat plates which are placed in parallel, the nozzle direction of a material cylinder for containing spinning solution is vertical to the long axis direction of the electrode, the nano-fibers sprayed out by the nozzle are lapped between the two metal flat plates and are uniformly arranged along the long axis direction vertical to the metal flat plates, and then the nano-fibers are overlapped layer by layer to form a crude product of the polymer nano-fiber film; during preparation, a laser diffraction device built by the user is adopted to detect the orientation degree of the polymer nanofiber in real time, and parameters of electrostatic spinning are adjusted in real time according to the detected orientation degree of the polymer nanofiber so as to realize high-orientation preparation of the polymer nanofiber;
s3, heating the crude product of the polymer nanofiber membrane prepared in the step S2, and stretching the crude product by 12 times at 150 ℃ to obtain the polymer nanofiber membrane.
Example 5
A preparation method of a polymer nanofiber membrane comprises the following steps:
s1, weighing 1 part by weight of polyacrylonitrile and 10 parts by weight of diethyl triamine, mixing and uniformly stirring at 100 ℃, and then stirring for 2 hours to prepare a spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by adopting a self-made parallel electrode; the parallel electrode is composed of two metal flat plates which are placed in parallel, the nozzle direction of a material cylinder for containing spinning solution is vertical to the long axis direction of the electrode, the nano-fibers sprayed out by the nozzle are lapped between the two metal flat plates and are uniformly arranged along the long axis direction vertical to the metal flat plates, and then the nano-fibers are overlapped layer by layer to form a crude product of the polymer nano-fiber film; during preparation, a laser diffraction device built by the user is adopted to detect the orientation degree of the polymer nanofiber in real time, and parameters of electrostatic spinning are adjusted in real time according to the detected orientation degree of the polymer nanofiber so as to realize high-orientation preparation of the polymer nanofiber;
s3, heating the crude product of the polymer nanofiber membrane prepared in the step S2, and stretching the crude product 8 times at 180 ℃ to obtain the polymer nanofiber membrane.
Example 6
A preparation method of a polymer nanofiber membrane comprises the following steps:
s1, weighing 1 part by weight of polyvinylidene fluoride and 30 parts by weight of dimethyl sulfoxide, mixing and uniformly stirring, and then performing oscillation treatment for 1 hour to prepare a spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by adopting a self-made parallel electrode; the parallel electrode is composed of two metal flat plates which are placed in parallel, the nozzle direction of a material cylinder for containing spinning solution is vertical to the long axis direction of the electrode, the nano-fibers sprayed out by the nozzle are lapped between the two metal flat plates and are uniformly arranged along the long axis direction vertical to the metal flat plates, and then the nano-fibers are overlapped layer by layer to form a crude product of the polymer nano-fiber film; during preparation, a laser diffraction device built by the user is adopted to detect the orientation degree of the polymer nanofiber in real time, and parameters of electrostatic spinning are adjusted in real time according to the detected orientation degree of the polymer nanofiber so as to realize high-orientation preparation of the polymer nanofiber;
s3, heating the crude product of the polymer nanofiber membrane prepared in the step S2, and stretching the crude product 8 times at 200 ℃ to obtain the polymer nanofiber membrane.
Example 7
A preparation method of a polymer nanofiber membrane comprises the following steps:
s1, weighing 1 part by weight of polyvinyl butyral and 50 parts by weight of dimethyl sulfoxide, mixing and uniformly stirring, and then carrying out ultrasonic treatment for 1 hour to prepare a spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by adopting a self-made parallel electrode; the parallel electrode is composed of two metal flat plates which are placed in parallel, the nozzle direction of a material cylinder for containing spinning solution is vertical to the long axis direction of the electrode, the nano-fibers sprayed out by the nozzle are lapped between the two metal flat plates and are uniformly arranged along the long axis direction vertical to the metal flat plates, and then the nano-fibers are overlapped layer by layer to form a crude product of the polymer nano-fiber film; during preparation, a laser diffraction device built by the user is adopted to detect the orientation degree of the polymer nanofiber in real time, and parameters of electrostatic spinning are adjusted in real time according to the detected orientation degree of the polymer nanofiber so as to realize high-orientation preparation of the polymer nanofiber;
s3, heating the crude product of the polymer nanofiber membrane prepared in the step S2, and stretching the crude product 10 times at 70 ℃ to obtain the polymer nanofiber membrane.
Comparative example 1
S1, weighing 1 part by weight of polyvinyl alcohol and 10 parts by weight of water, mixing and uniformly stirring, and then carrying out high-power ultrasonic treatment for half an hour at 800W to prepare a spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by adopting a self-made parallel electrode; the parallel electrode is composed of two metal flat plates which are placed in parallel, the nozzle direction of a material cylinder for containing spinning solution is vertical to the long axis direction of the electrode, the nano-fibers sprayed out by the nozzle are lapped between the two metal flat plates and are uniformly arranged along the long axis direction vertical to the metal flat plates, and then the nano-fibers are overlapped layer by layer to form a polymer nano-fiber film; in addition, the preparation method adopts a laser diffraction device to detect the orientation degree of the polymer nano-fiber in real time, and adjusts the parameter of electrostatic spinning in real time according to the detected orientation degree of the polymer nano-fiber so as to regulate and control the orientation degree of the polymer nano-fiber film.
Comparative example 2
A preparation method of a polymer nanofiber membrane comprises the following steps:
s1, weighing 1 part by weight of polyvinyl alcohol and 10 parts by weight of water, mixing and stirring uniformly, and then performing high-ultrasound treatment for half an hour at 800W to prepare a spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by using a large metal plate to obtain the polymer nanofiber membrane.
Comparative example 3
S1, weighing 1 part by weight of polyvinyl alcohol and 10 parts by weight of water, mixing and stirring uniformly, and then heating at 80 ℃ to dissolve to prepare spinning solution;
s2, performing electrostatic spinning on the spinning solution prepared in the step S1, and collecting the polymer nanofibers by using a large metal plate to obtain the polymer nanofiber membrane.
In order to further verify the performance of the polymer nanofiber membrane, the orientation and the thermal conductivity of the polymer nanofiber membrane prepared by the method are detected, and the method specifically comprises the following steps:
the molecular chain orientation of the polymer nanofiber films prepared in the above examples 1 to 7 and comparative examples 1 to 3 was measured by an X-ray diffractometer, and the results are shown in fig. 2 to 4, wherein (a), (b), (c), and (d) in fig. 2 are the wide-angle X-ray scattering spectra of the polymer nanofiber films prepared in examples 1, 2, 3, and 4, respectively; FIG. 3 (a), (b), and (c) are the wide-angle X-ray scattering spectra of the polymer nanofiber films prepared in examples 5, 6, and 7, respectively; in FIG. 4, (a), (b), and (c) are wide-angle X-ray scattering spectra of the polymer nanofiber films prepared in comparative examples 1, 2, and 3, respectively. The polymer nanofiber films prepared in comparative examples 1 and 2 were compared with a scanning electron microscope, and the results are shown in fig. 5, wherein (a) and (b) in fig. 5 are SEM images of the polymer nanofiber films prepared in comparative examples 1 and 2, respectively.
The differences among examples 1, 2, 3 and 4 are the differences in the stretch ratios, and as can be seen from fig. 2, the X-ray diffraction spots in the spectra gradually shrink with increasing stretch ratios, indicating that the orientation of the molecular chains in the nanofiber film is increasing; FIG. 3 shows that the X-ray diffraction patterns of the polymer nanofiber films prepared in examples 5-7 are in a large spot shape, rather than a half arc shape, and thus the molecular chains of the polymer nanofiber films of the above examples have relatively good orientation after the parallel electrodes are used and the thermal stretching is performed. As can be seen from fig. 4, in comparative example 1, the step of thermally stretching the polymer nanofiber film is omitted, and the X-ray diffraction spots are in a relatively large arc shape, indicating that the molecular chain orientation is relatively low; compared with the comparative example 1, the comparative example 2 only adopts one metal flat plate as a collecting device directly, the hot stretching treatment is omitted, the X-ray diffraction spots are closer to a semi-arc shape, and the molecular chain orientation is lower and the state is disordered; comparative example 3 is less in the process of treating the spinning solution with ultrasound than comparative example 2, and the X-ray diffraction spots are annular, which indicates that the molecular chains are almost completely disordered; comparison with the wide-angle X-ray spectrum in comparative example 2 shows that the ultrasound treatment of the spinning dope contributes to the orientation of the molecular chains. In addition, fig. 5 shows a comparison of SEM images of comparative example 1 and comparative example 2, and it was found that the fiber orientation in comparative example 1 having parallel electrodes as receiving means was relatively consistent, indicating that the introduction of parallel electrodes simultaneously increased the degree of orientation of molecular chain dimensions in the film and the alignment of the material at the fiber dimensions.
The thermal diffusivity of the polymer nanofiber films in the above examples and comparative examples is measured according to a built-up micro-nano scale thermophysical device based on the Angstrom method, then the specific heat capacity is measured by using a differential scanning calorimeter, the density is measured by using a density balance, and the thermal conductivity of each polymer nanofiber film is calculated according to the thermal diffusivity multiplied by the specific heat capacity multiplied by the density. The thermal conductivity of the polymer nanofiber thin films in the above examples and comparative examples is shown in table 1 below:
TABLE 1 thermal conductivity of Polymer nanofiber films
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Thermal conductivity W/m.K | 4.75 | 5.23 | 5.68 | 8.51 | 5.16 | 4.37 | 2.90 | 3.75 | 0.41 | 0.26 |
As can be seen from table 1 above, comparing comparative example 1 and comparative example 2, it is demonstrated that the increase of the degree of fiber orientation contributes to the improvement of the thermal conductivity; comparing comparative example 2 and comparative example 3, it is demonstrated that the increase in molecular chain orientation degree also contributes to the improvement in thermal conductivity; the comparative example further verifies that the thermal conductivity can be obviously increased along with the improvement of molecular chain orientation. The ordered arrangement of the molecular chains and the fiber two-stage structure in the film can realize the preparation of the high-heat-conductivity polymer film.
Claims (10)
1. The preparation method of the polymer nanofiber membrane is characterized by comprising the following steps:
s1, dissolving the insulating high molecular polymer in a solvent, and performing molecular chain unwrapping treatment in the dissolving process to prepare spinning solution;
s2, performing electrostatic spinning by using the spinning solution, and collecting the polymer nanofibers by using parallel electrodes to prepare a crude product of the polymer nanofiber membrane;
s3, carrying out hot stretching on the crude product of the polymer nanofiber membrane.
2. The method of claim 1, wherein in step S1, the molecular chain unwrapping process is an external force assisted unwrapping process.
3. The method for preparing a polymer nanofiber membrane as claimed in claim 2, wherein the external force assisted disentanglement treatment is at least one selected from ultrasonic treatment, oscillation treatment, vibration treatment, shearing treatment and stirring treatment.
4. The method of claim 1, wherein in step S1, the mass ratio of the insulating polymer to the solvent is 1: (1-50).
5. The method for preparing a polymer nanofiber membrane as claimed in claim 4, wherein the insulating polymer is at least one selected from polyethylene, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile and polyvinylidene fluoride.
6. The method of claim 4, wherein the solvent is at least one selected from the group consisting of water, diethyltriamine, triethylenetetramine, and dimethylsulfoxide.
7. The method for preparing a polymer nanofiber membrane as claimed in claim 1, wherein in step S1, the dissolution temperature in the dissolution process is 30-100 ℃.
8. The method for producing a polymer nanofiber membrane as claimed in claim 1, wherein in step S3, the drawing temperature of the hot drawing is 70 to 200 ℃.
9. The method of any one of claims 1 to 8, wherein in step S2, a fiber orientation degree detection device is used to detect the orientation degree of the polymer nanofibers in real time, and the electrostatic spinning parameters are adjusted in real time according to the detected orientation degree of the polymer nanofibers to control the orientation degree of the polymer nanofibers.
10. A polymer nanofiber membrane produced by the method for producing a polymer nanofiber membrane according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112144177A (en) * | 2020-09-27 | 2020-12-29 | 中国科学院过程工程研究所 | Polytetrafluoroethylene nanofiber membrane and preparation process thereof |
| CN115323612A (en) * | 2022-08-19 | 2022-11-11 | 佛山清立新材料科技有限公司 | High-thermal-conductivity composite material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230234A (en) * | 2011-06-24 | 2011-11-02 | 中国科学院上海应用物理研究所 | Synchrotron radiation in-situ on-line fiber spinning equipment |
| CN103211663A (en) * | 2012-08-13 | 2013-07-24 | 王深明 | Method for preparing electrospun artificial blood vessel with micro-nano biomimic intima structure |
| CN104711759A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院化学研究所 | Preparation method for poly L-lactic acid electrospinning film with stable fiber orientation structure |
| US20180240959A1 (en) * | 2014-12-30 | 2018-08-23 | University-Industry Cooperation Group Of Kyung Hee University | Nanofiber web piezoelectric material obtained by electrospinning polylactic acid, method of producing same, piezoelectric sensor comprising same, and method of manufacturing the piezoelectric sensor |
| CN110079936A (en) * | 2019-04-17 | 2019-08-02 | 厦门当盛新材料有限公司 | Fiber aftertreatment equipment and method are spun in a kind of sudden strain of a muscle |
| CN110846810A (en) * | 2019-10-09 | 2020-02-28 | 南方科技大学 | High-thermal-conductivity nano composite fiber film and preparation method thereof |
-
2020
- 2020-05-19 CN CN202010425809.4A patent/CN111705429A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230234A (en) * | 2011-06-24 | 2011-11-02 | 中国科学院上海应用物理研究所 | Synchrotron radiation in-situ on-line fiber spinning equipment |
| CN103211663A (en) * | 2012-08-13 | 2013-07-24 | 王深明 | Method for preparing electrospun artificial blood vessel with micro-nano biomimic intima structure |
| CN104711759A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院化学研究所 | Preparation method for poly L-lactic acid electrospinning film with stable fiber orientation structure |
| US20180240959A1 (en) * | 2014-12-30 | 2018-08-23 | University-Industry Cooperation Group Of Kyung Hee University | Nanofiber web piezoelectric material obtained by electrospinning polylactic acid, method of producing same, piezoelectric sensor comprising same, and method of manufacturing the piezoelectric sensor |
| CN110079936A (en) * | 2019-04-17 | 2019-08-02 | 厦门当盛新材料有限公司 | Fiber aftertreatment equipment and method are spun in a kind of sudden strain of a muscle |
| CN110846810A (en) * | 2019-10-09 | 2020-02-28 | 南方科技大学 | High-thermal-conductivity nano composite fiber film and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112144177A (en) * | 2020-09-27 | 2020-12-29 | 中国科学院过程工程研究所 | Polytetrafluoroethylene nanofiber membrane and preparation process thereof |
| CN115323612A (en) * | 2022-08-19 | 2022-11-11 | 佛山清立新材料科技有限公司 | High-thermal-conductivity composite material and preparation method thereof |
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