CN113851329B - Method for improving surface charge storage stability of polyolefin film - Google Patents
Method for improving surface charge storage stability of polyolefin film Download PDFInfo
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- CN113851329B CN113851329B CN202111119919.9A CN202111119919A CN113851329B CN 113851329 B CN113851329 B CN 113851329B CN 202111119919 A CN202111119919 A CN 202111119919A CN 113851329 B CN113851329 B CN 113851329B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
- H01G7/021—Electrets, i.e. having a permanently-polarised dielectric having an organic dielectric
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for improving the surface charge storage stability of a polyolefin film, which is characterized by comprising the following steps: drying the polyolefin film in a vacuum box, and placing the polyolefin film in a NaOH solution for activation, so that the surface of the polyolefin film is hydrolyzed to generate active hydroxyl groups; immersing the activated polyolefin film in phosphoric acid solution, standing on a heating plate, and heating for reaction; repeatedly cleaning the polyolefin film after the reaction is completed by deionized water and absolute ethyl alcohol, and then drying the polyolefin film in a vacuum box; the dried polyolefin film was subjected to testing of infrared spectrum, X-ray photoelectron spectrum and surface potential attenuation characteristics before and after modification at room temperature. The method is simple and feasible, is simple to operate, has low cost, requires low tool cost, has good practicability, and can improve the surface charge storage stability of the polyolefin film by introducing inorganic phosphorus-containing groups on the surface of the polyolefin.
Description
Technical Field
The invention relates to the technical research field of engineering dielectrics and electrical engineering, in particular to the field of polyolefin film surface charge storage.
Background
The polyolefin film has the characteristics of low dielectric loss, excellent mechanical property, easy processing, low cost and the like, and is a high polymer material with excellent properties, so that the polyolefin film is widely applied to the fields of power electronics, aerospace, precision machinery and the like. Polyolefin films have attracted considerable attention as electret materials which should have the ability to store charges stably for a long period of time, however, in some applications where the voltage level is high, the surface insulation properties of the polyolefin have not been satisfactory.
In chinese patent CN107051230a, a method for improving the performance of purifying aged oil by using a filter membrane is disclosed, and specifically: 1) placing the filter membrane in a vacuum drying oven for vacuum drying at the drying temperature of 40-80 ℃ for 4-48 hours, so as to remove water in the filter membrane, 2) carrying out fluorination treatment on the filter membrane by a surface modification method, forming a fluorinated layer on the surface of the filter membrane, 3) cleaning a sand core hopper … … by adopting absolute ethyl alcohol, deionized water and an ultrasonic cleaner, respectively installing the filter membrane which is not subjected to fluorination treatment and the filter membrane which is subjected to fluorination treatment in the sand core hopper, filtering aging oil, and measuring unfiltered and filtered oil samples by a frequency dielectric spectrum method. Wherein the filter membrane adopts a polypropylene or PTEE filter membrane.
In the above patents, polypropylene or PTEE filters are modified so that their performance in application to filtration of transformer oils is improved. The main steps are to carry out fluorination treatment.
However, the application fields of the polypropylene or PTEE filter membranes in the above patents are inconsistent with the application, and the technical problems to be solved are different. Therefore, the preparation of the polyolefin film with high charge storage stability has important significance for practical application of the polyolefin film.
Disclosure of Invention
The invention aims to provide a method for improving the surface charge storage stability of a polyolefin film.
In order to achieve the above object, the present invention is provided as follows: a method for improving the surface charge storage stability of a polyolefin film comprising the steps of: (1) Drying the polyolefin film in a vacuum box, and placing the polyolefin film in a NaOH solution for activation, so that the surface of the polyolefin film is hydrolyzed to generate active hydroxyl groups; (2) Immersing the polyolefin film activated in the step (1) in a phosphoric acid solution, and standing on a heating plate for heating reaction; (3) Repeatedly cleaning the polyolefin film after the reaction in the step (2) with deionized water and absolute ethyl alcohol, and then drying in a vacuum box again; (4) Testing infrared spectrum, X-ray photoelectron spectrum and surface potential attenuation characteristics of the polyolefin film dried in the step (3) before and after modification at room temperature
Wherein, the polyolefin film in the step (1) is placed in a vacuum drying oven for drying at 60 ℃ for 12 hours, and then is placed in a NaOH solution with the concentration of 1mol/L for activation for 30 minutes.
Wherein, the polyolefin film in the step (2) is immersed in 85wt% phosphoric acid solution and is left to react for 24 hours at 120 ℃ on a heating plate.
Wherein, the polyolefin film in the step (3) is repeatedly washed by deionized water and absolute ethyl alcohol and then is placed in a vacuum drying oven at 60 ℃ for drying for 12 hours.
And (2) repeatedly flushing the surface of the polyolefin film in the step (1) with deionized water and absolute ethyl alcohol after the polyolefin film is activated to remove other products of the reaction, and drying the film in a vacuum drying oven at 60 ℃ for 6 hours.
The polyolefin film may be biaxially oriented polypropylene film, low-density polyethylene film, high-density polyethylene film or polytetrafluoroethylene film.
Preferably, the polyolefin film has a thickness of 10 μm.
Further, in the step (4), the surface potential of the polyolefin film is tested by adopting a surface potential attenuation platform, the film is charged for 10min by applying-3 kV direct-current voltage, the testing time is 30000s, and the testing temperature is 25 ℃.
The beneficial effects are that:
the method is simple and feasible, is simple to operate, has low cost, requires low tool cost, has good practicability, and can improve the surface charge storage stability of the polyolefin film by introducing inorganic phosphorus-containing groups on the surface of the polyolefin. And the method for realizing the surface charge storage stability of the polyolefin film can be realized only by heating the platform and the oven.
Drawings
The drawings of the present invention are described below.
FIG. 1 is a Fourier IR spectrum of a polypropylene film before and after treatment according to the present invention;
FIG. 2 shows XPS analysis of polypropylene films before and after processing according to the present invention;
FIG. 3 shows the surface potential decay characteristics of polypropylene films before and after treatment according to the present invention.
Detailed Description
Embodiments of the present application are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application. On the contrary, the embodiments of the present application include all alternatives, modifications, and equivalents as may be included within the spirit and scope of the appended claims.
Example 1: the embodiment of the application provides a method for improving the surface charge storage stability of a polyolefin film, which comprises the following steps:
(1) Drying the polyolefin film in a vacuum box, and placing the polyolefin film in a NaOH solution for activation, so that the surface of the polyolefin film is hydrolyzed to generate active hydroxyl groups; (2) Immersing the polyolefin film activated in the step (1) in a phosphoric acid solution, and standing on a heating plate for heating reaction; (3) Repeatedly cleaning the polyolefin film after the reaction in the step (2) with deionized water and absolute ethyl alcohol, and then drying in a vacuum box again; (4) Testing infrared spectrum, X-ray photoelectron spectrum and surface potential attenuation characteristics of the polyolefin film dried in the step (3) before and after modification at room temperature
Wherein, the polyolefin film in the step (1) is placed in a vacuum drying oven for drying at 60 ℃ for 12 hours, and then is placed in a NaOH solution with the concentration of 1mol/L for activation for 30 minutes. The polyolefin film in the step (2) was immersed in 85wt% phosphoric acid solution and left to react on a heating plate at 120℃for 24 hours. And (3) repeatedly cleaning the polyolefin film in the step (3) by deionized water and absolute ethyl alcohol, and then drying the polyolefin film in a vacuum drying oven at 60 ℃ for 12 hours. And (3) testing the surface potential of the polyolefin film by adopting a surface potential attenuation platform in the step (4), and charging the film by applying-3 kV direct current voltage for 10min, wherein the testing time is 30000s, and the testing temperature is 25 ℃.
As another embodiment in this example, after the polyolefin film in the step (1) is activated, the surface of the film is repeatedly rinsed with deionized water and absolute ethyl alcohol to remove other products of the reaction, and the film is dried at 60 ℃ for 6 hours in a vacuum drying oven, and then the step (2) is performed.
In this embodiment, the polyolefin film may use a biaxially oriented polypropylene film, a low density polyethylene film, a high density polyethylene film, or a polytetrafluoroethylene film. As a preferred mode in this embodiment, the polyolefin film has a thickness of 10. Mu.m.
The method of the embodiment is simple and feasible, is simple to operate, has low cost, requires low tool cost, has good practicability, and can improve the surface charge storage stability of the polyolefin film by introducing inorganic phosphorus-containing groups on the surface of the polyolefin. And the method for realizing the surface charge storage stability of the polyolefin film can be realized only by heating the platform and the oven.
Example 2: the embodiment of the application provides a method for improving the surface charge storage stability of a biaxially oriented polypropylene film, which comprises the following steps:
(1) Placing the biaxially oriented polypropylene film in a vacuum drying oven to be dried for 12 hours at 60 ℃; (2) Placing the cleaned and dried polypropylene film in a 1mol/L NaOH solution, and treating for 0.5h at normal temperature to activate the surface of the polypropylene film; (3) Repeatedly cleaning the polypropylene film by using deionized water and absolute ethyl alcohol after the treatment is finished so as to remove other products of the reaction, and drying the polypropylene film for 6 hours at the temperature of 60 ℃ in a vacuum drying oven; (4) Placing the dried film in phosphoric acid with the mass fraction of 85%, wherein the treatment temperature is 120 ℃, and the treatment time is 24 hours; (5) After the treatment is finished, repeatedly cleaning the polypropylene film by using deionized water and absolute ethyl alcohol to remove other products of the reaction; (6) Finally, the film is dried for 12 hours in a vacuum drying oven at 60 ℃.
FIG. 1 is a Fourier infrared spectrum of the film before and after the treatment by the method in the embodiment, and the sample after the phosphating treatment shows an obvious wide absorption peak at a wave number of 1125cm < -1 >, which shows that the surface of the polypropylene film is hydrolyzed to generate active hydroxyl (-OH) groups so as to achieve a better phosphating treatment effect. The film after phosphating treatment causes the absorption peak corresponding to the molecular chain fracture C-H bond stretching vibration (2700-3000 cm < -1 > and 1300-1500cm < -1 >) to be obviously attenuated. Meanwhile, P-O-C bonds are formed in the wave number range of 900-1125cm-1, which indicates that the phosphorylation modification has introduced a large number of phosphate groups on the surface of the sample.
FIG. 2 is an X-ray photoelectron spectrum of the film before and after the treatment by the method, wherein (a) and (b) are fine spectra of C1s bond and P2P. From the graph, the C1s spectrum has a stronger main peak at 284.6eV, the main peak is obviously reduced after phosphating treatment, and a weak peak corresponding to C=O bond appears at 288.3eV, which indicates that the C-C bond or C-H bond on the surface of the sample is broken after phosphating treatment to generate a new energy spectrum peak. Correspondingly, the sample after phosphating showed a distinct P2P peak at 133.5 eV.
Fig. 3 shows the surface potential decay characteristics of the film before and after the treatment by the method, and as can be seen from the graph, after 30000s of charge decay, the surface charge decay of the unmodified sample is 49% of the initial value, and the charge decay of the modified sample is 66% of the initial value, so that the surface charge decay rate of the surface modified sample is much slower than that of the unmodified sample, and the surface charge stability is significantly improved.
Of course, the polypropylene examples of the present invention are only illustrative and not restrictive, and although the present invention has been described in detail with reference to the foregoing examples, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing examples, or that equivalents may be substituted for some of the technical features thereof, for example, substitution of polypropylene for other polyethylene, polytetrafluoroethylene or other polyolefin films. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Finally, it is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (6)
1. A method for improving the surface charge storage stability of a polyolefin film comprising the steps of:
(1) Drying the polyolefin film for 12 hours at 60 ℃ in a vacuum box, and then placing the polyolefin film into a 1mol/L NaOH solution for activation for 30 minutes to hydrolyze the surface of the polyolefin film to generate active hydroxyl groups;
(2) Immersing the polyolefin film activated in the step (1) in 85wt% phosphoric acid solution, standing on a heating plate for heating reaction, and reacting at 120 ℃ for 24 hours;
(3) Repeatedly cleaning the polyolefin film after the reaction in the step (2) with deionized water and absolute ethyl alcohol, and then drying in a vacuum box again;
(4) And (3) carrying out testing on infrared spectrum, X-ray photoelectron spectrum and surface potential attenuation characteristics before and after modification on the polyolefin film dried in the step (3) at room temperature.
2. A method of improving the surface charge storage stability of a polyolefin film according to claim 1, wherein: wherein, the polyolefin film in the step (3) is repeatedly washed by deionized water and absolute ethyl alcohol and then is placed in a vacuum drying oven at 60 ℃ for drying for 12 hours.
3. A method of improving the surface charge storage stability of a polyolefin film according to claim 2, wherein: and (2) repeatedly flushing the surface of the polyolefin film in the step (1) with deionized water and absolute ethyl alcohol after the polyolefin film is activated to remove other products of the reaction, and drying the film in a vacuum drying oven at 60 ℃ for 6 hours.
4. A method of improving the surface charge storage stability of a polyolefin film according to claim 1, 2 or 3, wherein: the polyolefin film is a biaxially oriented polypropylene film, a low-density polyethylene film, a high-density polyethylene film or a polytetrafluoroethylene film.
5. A method of improving the surface charge storage stability of a polyolefin film according to claim 1, 2 or 3, wherein: the polyolefin film thickness was 10 μm.
6. A method of improving the surface charge storage stability of a polyolefin film according to claim 1, 2 or 3, wherein: and (3) testing the surface potential of the polyolefin film by adopting a surface potential attenuation platform in the step (4), and charging the film by applying-3 kV direct current voltage for 10min, wherein the testing time is 30000s, and the testing temperature is 25 ℃.
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Citations (4)
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| US6420024B1 (en) * | 2000-12-21 | 2002-07-16 | 3M Innovative Properties Company | Charged microfibers, microfibrillated articles and use thereof |
| JP2021097213A (en) * | 2019-12-13 | 2021-06-24 | 株式会社デンソー | Electret |
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| GB1006622A (en) * | 1962-07-18 | 1965-10-06 | Toyo Rayon Co Ltd | Method of improving the surface properties of polypropylene film |
| EP0623941B1 (en) * | 1993-03-09 | 1997-08-06 | Hoechst Celanese Corporation | Polymer electrets with improved charge stability |
| DE10235571A1 (en) * | 2002-08-03 | 2004-02-12 | Clariant Gmbh | New magnesium-aluminum hydroxide-carbonates with sebacic acid anions and use of foliated double hydroxide salt as charge regulator in electrophotographic toner or developer, powder lacquer, electret or electrostatic separation |
| JP2014060146A (en) * | 2012-08-23 | 2014-04-03 | Toray Ind Inc | Porous polyolefin film, and electric power storage device |
| CN105111489B (en) * | 2015-08-31 | 2018-06-29 | 重庆大学 | In the method that Kapton surface introduces phosphorus-containing groups |
| CN111830086A (en) * | 2020-05-07 | 2020-10-27 | 西安电子科技大学 | Preparation method of gas sensor based on polyaniline film surface modification |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1258638A (en) * | 1968-04-27 | 1971-12-30 | ||
| US3632443A (en) * | 1968-04-27 | 1972-01-04 | Sony Corp | Method of making polypropylene electrets |
| DE19725253A1 (en) * | 1997-06-13 | 1998-12-17 | Hoechst Ag | Electrets containing cyclo-olefin] copolymers |
| US6420024B1 (en) * | 2000-12-21 | 2002-07-16 | 3M Innovative Properties Company | Charged microfibers, microfibrillated articles and use thereof |
| JP2021097213A (en) * | 2019-12-13 | 2021-06-24 | 株式会社デンソー | Electret |
Non-Patent Citations (1)
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