CN110951195A - PMMA/PVDF composite film and preparation method thereof - Google Patents

PMMA/PVDF composite film and preparation method thereof Download PDF

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CN110951195A
CN110951195A CN201911251052.5A CN201911251052A CN110951195A CN 110951195 A CN110951195 A CN 110951195A CN 201911251052 A CN201911251052 A CN 201911251052A CN 110951195 A CN110951195 A CN 110951195A
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pmma
composite film
pvdf
temperature
pvdf composite
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迟庆国
殷超
张天栋
冯宇
张月
张永泉
张昌海
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Harbin University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract

The invention relates to a PMMA/PVDF composite film and a preparation method thereof, belonging to the technical field of polymer-based dielectric materials. In order to solve the problem that the existing polymer-based dielectric material is low in breakdown field strength and energy storage density, the invention provides a PMMA/PVDF composite film, which is prepared by blending and hot-pressing a linear polymer PMMA and a ferroelectric polymer PVDF, wherein the volume percentage of PMMA in the composite film is 25-75 vol%. The composite film prepared by the invention has good dielectric constant, breakdown field strength of 570kV/mm and energy storage density of 20.08J/cm3Lower loss and leakage current density, and conventional polyCompared with the compound-based dielectric material, the compound-based dielectric material has the advantages of obviously reduced breakdown probability, good insulating property, and capability of being applied to the manufacture of energy storage devices and improving the energy storage and breakdown characteristics of dielectric capacitors.

Description

PMMA/PVDF composite film and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer-based dielectric materials, and particularly relates to a PMMA/PVDF composite film and a preparation method thereof.
Background
The polymer-based dielectric capacitor has the advantages of high power density, high open-circuit voltage, good flexibility and the like, and has wide application prospects in the military and civil fields of new energy automobiles, electromagnetic ejection and the like. With the continuous development of the electrical and electronic engineering field, the requirement for the energy storage characteristic of the dielectric capacitor is also increased day by day. The energy storage capacity of the dielectric capacitor depends on the strength of the performance of the dielectric material filled in the dielectric capacitor, and the polymer material is widely researched due to the excellent electrical insulation property, the good mechanical property and the lower dielectric loss.
At present, most polymer materials have higher breakdown electric fields but lower dielectric constants, and ferroelectric polymers represented by polyvinylidene fluoride (PVDF) are expected to become novel composite films with high energy storage characteristics due to unique thermoelectric, piezoelectric, dielectric and chemical resistance performances, but the dielectric loss of the ferroelectric polymers is higher under an external electric field, so that the charge-discharge efficiency of the composite films is lower. Meanwhile, the linear polymer polymethyl methacrylate (PMMA) has high breakdown field strength and energy storage efficiency, but the low dielectric constant makes it difficult to obtain high energy storage density.
Disclosure of Invention
The invention provides a PMMA/PVDF composite film and a preparation method thereof, aiming at solving the problems of low breakdown field strength and low energy storage density of the existing polymer-based dielectric material.
The technical scheme of the invention is as follows:
a PMMA/PVDF composite film is prepared by blending and hot-pressing a linear polymer PMMA and a ferroelectric polymer PVDF, wherein the volume percentage of PMMA in the composite film is 25-75 vol%.
Further, the PMMA accounts for 50 vol% of the composite film.
Furthermore, the thickness of the composite film is 10-20 μm.
The invention provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
preparing PMMA, N-dimethylformamide-DMF solution and PVDF according to a certain mass-volume ratio, adding PMMA into the DMF solution for multiple times, stirring until the solution is clear, adding PVDF into the clear solution for multiple times, and stirring at a certain temperature to obtain a uniform colloid blended by PMMA and PVDF;
step two, stirring the blended colloid obtained in the step one under vacuum for a certain time, then carrying out vacuum pumping treatment at room temperature and standing for a certain time, blade-coating the standing blended colloid on a glass substrate by using a tape casting method, placing the glass substrate with the blended colloid under a certain temperature for heat treatment for a certain time, and removing an organic solvent to obtain a PMMA/PVDF composite membrane;
and step three, carrying out hot-pressing treatment on the PMMA/PVDF composite film obtained in the step two by adopting a hot-pressing process to obtain a compact PMMA/PVDF composite film.
Furthermore, the mass-volume ratio of the PMMA solution to the DMF solution to the PVDF in the step one is (0.02-0.30) g to 1mL (0.08-0.20) g.
Further, in the step one, the stirring temperature is 30-70 ℃, and the stirring time is 8-15 hours.
Further, the blending colloid in the second step is stirred in vacuum for 2-5 h, standing time is 8-10 h, and vacuum degrees of vacuum stirring and vacuum pumping treatment are 0.085-0.095 MPa.
Furthermore, the blade coating speed of the tape casting method in the second step is 1-3 cm/s, and the thickness of a blade coating wet film is 15-35 mu m.
Further, the heat treatment temperature of the glass substrate with the blended colloid in the second step is 60-200 ℃, and the heat treatment time is 12-20 hours.
Further, the hot pressing treatment in the third step is gradient hot pressing treatment, the hot pressing temperature in the first stage is 90-140 ℃, and the pressure is maintained for 20-80 min under 1-7 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept at 140-170 ℃ for 40-60 min after pressure relief so as to remove air bubbles in the composite film; the hot pressing temperature in the third stage is 140-170 ℃, and the pressure is maintained for 10-30 min under 10-20 MPa; and cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 1-5 min at 1-15 MPa.
The invention has the beneficial effects that:
the method utilizes the polarization characteristics of PMMA and PVDF, and prepares the PMMA/PVDF composite film based on the ferroelectric and linear polymer blending strategy, the composite film has good dielectric constant and breakdown field strength, the PMMA/PVDF composite film with the heat treatment temperature of 150 ℃ and the PMMA content of 50 vol% has higher breakdown field strength (570-570)
kV/mm) and energy storage density (-20.08J/cm)3) Compared with the traditional polymer-based dielectric material, the dielectric capacitor has the advantages that the breakdown probability is obviously reduced, and the energy storage and breakdown characteristics of the dielectric capacitor can be improved.
The PMMA/PVDF composite film prepared by the invention has lower loss and leakage current density and good insulating property, and can be applied to the manufacture of energy storage devices.
The method has the advantages of simple and convenient process flow, environmental protection, no pollution, low equipment price and suitability for large-scale production.
Drawings
FIG. 1 is an X-ray diffraction pattern of films prepared in examples 9, 12 to 15 and comparative examples 1 and 2;
FIG. 2 is a scanning electron micrograph of Pure PVDF-150 ℃ Pure PVDF prepared in comparative example 2;
FIG. 3 is a scanning electron microscope image of 50% PMMA at-120 ℃ of the PMMA/PVDF composite film prepared in example 12;
FIG. 4 is a scanning electron microscope image of-150 ℃ 25% PMMA of the PMMA/PVDF composite film prepared in example 14;
FIG. 5 is a scanning electron microscope image of-150 ℃ 50% PMMA of the PMMA/PVDF composite film prepared in example 9;
FIG. 6 is a scanning electron microscope image of the PMMA/PVDF composite film prepared in example 15, at-150 ℃ and 75% PMMA;
FIG. 7 is a scanning electron micrograph of a PMMA/PVDF composite film prepared in example 13 at-175 ℃ with 50% PMMA;
FIG. 8 is a scanning electron micrograph of Pure PMMA film prepared in comparative example 1- -150 ℃ Pure PMMA;
FIG. 9 is a graph of the dielectric properties of films prepared in examples 9, 14, 15 and comparative examples 1, 2;
FIG. 10 is a graph of the dielectric properties of films prepared in examples 9, 12, 13 and comparative examples 1, 2;
FIG. 11 is a Weibull plot of breakdown field strengths of films prepared in examples 9, 14, 15 and comparative examples 1, 2;
FIG. 12 is a Weibull plot of breakdown field strengths of films prepared in examples 9, 12, 13 and comparative examples 1, 2;
FIG. 13 is a graph of the energy storage performance of the films prepared in examples 9, 14, 15 and comparative examples 1, 2;
fig. 14 is a graph showing the energy storage properties of the thin films prepared in examples 9, 12, and 13 and comparative examples 1 and 2.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
A PMMA/PVDF composite film is prepared by blending and hot-pressing a linear polymer PMMA and a ferroelectric polymer PVDF, wherein the volume percentage of PMMA in the composite film is 25-75 vol%.
Example 2
A PMMA/PVDF composite film is prepared by blending and hot-pressing a linear polymer PMMA and a ferroelectric polymer PVDF, wherein the volume percentage of PMMA in the composite film is 25 vol%, and the thickness of the composite film is 10-20 mu m.
Example 3
A PMMA/PVDF composite film is prepared by blending and hot-pressing a linear polymer PMMA and a ferroelectric polymer PVDF, wherein the volume percentage of PMMA in the composite film is 50 vol%, and the thickness of the composite film is 10-20 mu m.
Example 4
A PMMA/PVDF composite film is prepared by blending and hot-pressing a linear polymer PMMA and a ferroelectric polymer PVDF, wherein the volume percentage of PMMA in the composite film is 75 vol%, and the thickness of the composite film is 10-20 mu m.
Example 5
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
preparing PMMA, DMF solution and PVDF according to a certain mass-volume ratio, adding PMMA into the DMF solution for multiple times, stirring until the mixture is clear, adding PVDF into the clear solution for multiple times, and stirring at a certain temperature to obtain a uniform colloid blended by PMMA and PVDF;
step two, stirring the blended colloid obtained in the step one under vacuum for a certain time, then carrying out vacuum pumping treatment at room temperature and standing for a certain time, blade-coating the standing blended colloid on a glass substrate by using a tape casting method, placing the glass substrate with the blended colloid under a certain temperature for heat treatment for a certain time, and removing an organic solvent to obtain a PMMA/PVDF composite membrane;
and step three, carrying out hot-pressing treatment on the PMMA/PVDF composite film obtained in the step two by adopting a hot-pressing process to obtain a compact PMMA/PVDF composite film.
Example 6
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
preparing PMMA, a DMF solution and PVDF according to the mass-to-volume ratio of (0.02-0.30) g:1mL (0.08-0.20), adding PMMA into the DMF solution for multiple times, stirring until the mixture is clarified, adding PVDF into the clarified solution for multiple times, and stirring for 8-15 hours at the temperature of 30-70 ℃ to obtain a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blend colloid obtained in the step one for 2-5 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 8-10 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are 0.085-0.095 MPa. Scraping the standing blend colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 1-3 cm/s, the thickness of a scraping wet film is 15-35 mu m, placing the glass substrate with the blend colloid at the temperature of 60-200 ℃ for heat treatment for 12-20 h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 90-140 ℃, and the pressure is maintained for 20-80 min at 1-7 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept at 140-170 ℃ for 40-60 min after pressure relief so as to remove air bubbles in the composite film; the hot pressing temperature in the third stage is 140-170 ℃, and the pressure is maintained for 10-30 min under 10-20 MPa; and cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 1-5 min at 1-15 MPa. Obtaining the compact PMMA/PVDF composite film.
Example 7
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 1.5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2.235g of PVDF into the clear solution for multiple times, and stirring for 8 hours at the temperature of 30 ℃ to obtain a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 2 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 8 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 1cm/s, the thickness of a scraping wet film is 20-25 mu m, placing the glass substrate with the blended colloid at the temperature of 60 ℃ for heat treatment for 20h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 90 ℃, and the pressure is maintained for 20min at 7 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 40min at 140 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 140 ℃, and the pressure is maintained for 10min under 10 MPa; and cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 5min at 1MPa to obtain the compact PMMA/PVDF composite film.
Example 8
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 1.5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2.235g of PVDF into the clear solution for multiple times, and stirring for 10 hours at the temperature of 40 ℃ to obtain a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 3 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 8 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 2cm/s, the thickness of a scraping wet film is 20-25 mu m, placing the glass substrate with the blended colloid at the temperature of 80 ℃ for heat treatment for 18h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 100 ℃, and the pressure is maintained for 20min at 7 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 45min at 145 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 150 ℃, and the pressure is maintained for 15min under 12 MPa; and cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 4min at 5MPa to obtain a compact PMMA/PVDF composite film.
Example 9
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 1.5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2.235g of PVDF into the clear solution for multiple times, and stirring for 12 hours at the temperature of 50 ℃ to obtain a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 4 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 9 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 3cm/s, the thickness of a scraping wet film is 20-25 mu m, placing the glass substrate with the blended colloid at the temperature of 150 ℃ for heat treatment for 16h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 140 ℃, and the pressure is maintained for 25min at 6 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 50min at 150 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 170 ℃, and the pressure is maintained for 20min under 15 MPa; and then cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 4min at 8MPa to obtain the compact PMMA/PVDF composite film, namely 50 percent PMMA at the temperature of-150 ℃.
Example 10
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 1.5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2.235g of PVDF into the clear solution for multiple times, and stirring for 14 hours at the temperature of 60 ℃ to prepare a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 5 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 9 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 2cm/s, the thickness of a scraping wet film is 15-35 mu m, placing the glass substrate with the blended colloid at the temperature of 100 ℃ for heat treatment for 18h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 120 ℃, and the pressure is maintained for 60min at 3 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 55min at 160 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 160 ℃, and the pressure is maintained for 25min under 17 MPa; and cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 3min at 12MPa to obtain a compact PMMA/PVDF composite film.
Example 11
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 1.5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2.235g of PVDF into the clear solution for multiple times, and stirring for 15 hours at the temperature of 70 ℃ to prepare a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 5 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 10 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 2cm/s, the thickness of a scraping wet film is 20-25 mu m, placing the glass substrate with the blended colloid at the temperature of 200 ℃ for heat treatment for 12h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 130 ℃, and the pressure is maintained for 80min under 1 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 60min at 170 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 170 ℃, and the pressure is maintained for 30min under 20 MPa; and cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 1min at 15MPa to obtain a compact PMMA/PVDF composite film.
Example 12
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 1.5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2.235g of PVDF into the clear solution for multiple times, and stirring for 12 hours at the temperature of 50 ℃ to obtain a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 4 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 9 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 3cm/s, the thickness of a scraping wet film is 20-25 mu m, placing the glass substrate with the blended colloid at the temperature of 120 ℃ for heat treatment for 16h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 140 ℃, and the pressure is maintained for 25min at 6 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 50min at 150 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 170 ℃, and the pressure is maintained for 20min under 15 MPa; and then cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 4min at 8MPa to obtain the compact PMMA/PVDF composite film, namely 50 percent PMMA at the temperature of-120 ℃.
Example 13
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 1.5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2.235g of PVDF into the clear solution for multiple times, and stirring for 12 hours at the temperature of 50 ℃ to obtain a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 4 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 9 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 3cm/s, the thickness of a scraping wet film is 20-25 mu m, placing the glass substrate with the blended colloid at 175 ℃ for heat treatment for 16h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 140 ℃, and the pressure is maintained for 25min at 6 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 50min at 150 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 170 ℃, and the pressure is maintained for 20min under 15 MPa; and then cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 4min at 8MPa to obtain the compact PMMA/PVDF composite film which is 50 percent of PMMA at the temperature of 175 ℃.
Example 14
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 0.447g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2g of PVDF into the clear solution for multiple times, and stirring for 12 hours at the temperature of 50 ℃ to obtain a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 4 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 9 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 3cm/s, the thickness of a scraping wet film is 20-25 mu m, placing the glass substrate with the blended colloid at the temperature of 150 ℃ for heat treatment for 16h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 140 ℃, and the pressure is maintained for 25min at 6 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 50min at 150 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 170 ℃, and the pressure is maintained for 20min under 15 MPa; and then cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 4min at 8MPa to obtain compact PMMA/PVDF composite film, wherein the PMMA content is 25% at the temperature of-150 ℃.
Example 15
The embodiment provides a preparation method of a PMMA/PVDF composite film, which comprises the following steps:
step one, adding 5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, adding 2.486g of PVDF into the clear solution for multiple times, and stirring for 12 hours at the temperature of 50 ℃ to obtain a uniform colloid blended by PMMA and PVDF;
and step two, stirring the blended colloid obtained in the step one for 4 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 9 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Scraping the standing blended colloid onto a glass substrate by using a tape casting method, wherein the scraping speed is 3cm/s, the thickness of a scraping wet film is 20-25 mu m, placing the glass substrate with the blended colloid at the temperature of 150 ℃ for heat treatment for 16h, and removing an organic solvent to obtain a PMMA/PVDF composite film;
step three, carrying out hot pressing treatment on the PMMA/PVDF composite membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 140 ℃, and the pressure is maintained for 25min at 6 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 50min at 150 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 170 ℃, and the pressure is maintained for 20min under 15 MPa; and then cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 4min at 8MPa to obtain the compact PMMA/PVDF composite film which is 75 percent of PMMA at the temperature of-150 ℃.
Comparative example 1
The comparative example provides a method for preparing a PMMA film, comprising the following steps:
step one, adding 1.5g of PMMA into 20mL of DMF solution for multiple times, stirring until the solution is clear, and stirring for 12 hours at the temperature of 50 ℃ to obtain PMMA colloid;
and step two, stirring the PMMA colloid obtained in the step one for 4 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 9 hours, wherein the vacuum degree of the vacuum stirring and vacuum pumping treatment is 0.09 MPa. Coating the settled PMMA colloid on a glass substrate by using a tape casting method, wherein the coating speed is 3cm/s, the thickness of a coated wet film is 20-25 mu m, placing the glass substrate with the PMMA colloid at the temperature of 150 ℃ for heat treatment for 16h, and removing an organic solvent to obtain a PMMA film;
step three, carrying out hot pressing treatment on the PMMA film obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 140 ℃, and the pressure is maintained for 25min at 6 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 50min at 150 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 170 ℃, and the pressure is maintained for 20min under 15 MPa; and cooling the temperature of the PMMA film to room temperature by water cooling, and maintaining the pressure for 4min at 8MPa to obtain the compact PMMA film, namely the pure PMMA at the temperature of-150 ℃.
Comparative example 2
The comparative example provides a preparation method of a PVDF film, comprising the following steps:
step one, adding 2.235g of PVDF into 20mL of DMF solution for multiple times, and stirring at 50 ℃ for 12 hours to prepare PVDF colloid;
and step two, stirring the PVDF colloid obtained in the step one for 4 hours under vacuum, then carrying out vacuum pumping treatment at room temperature and standing for 9 hours, wherein the vacuum degrees of the vacuum stirring and the vacuum pumping treatment are both 0.09 MPa. Coating the settled PVDF colloid on a glass substrate by a tape casting method at a coating speed of 3cm/s and a coating wet film thickness of 20-25 mu m, placing the glass substrate with the PVDF colloid at the temperature of 150 ℃ for heat treatment for 16h, and removing an organic solvent to obtain a PVDF composite film;
step three, carrying out hot pressing treatment on the PVDF membrane obtained in the step two by adopting a hot pressing process, wherein the hot pressing treatment is gradient hot pressing treatment, the hot pressing temperature in the first stage is 140 ℃, and the pressure is maintained for 25min at 6 MPa; in the second stage, pressure relief treatment is carried out, and the temperature is kept for 50min at 150 ℃ after pressure relief so as to remove air bubbles inside the composite film; the hot pressing temperature in the third stage is 170 ℃, and the pressure is maintained for 20min under 15 MPa; and then cooling the temperature of the obtained PVDF film to room temperature through water cooling, and maintaining the pressure for 4min at 8MPa to obtain the compact PVDF film which is pure PVDF at the temperature of-150 ℃.
FIG. 1 is an X-ray diffraction pattern of films prepared in examples 9 and 12 to 15 and comparative examples 1 and 2. from FIG. 1, it can be seen that the intensity of the α phase diffraction peak of PVDF in the PMMA/PVDF composite film decreases with increasing PMMA content and finally the diffraction peak almost disappears. the intensity of the β phase diffraction peak of PVDF in the PMMA/PVDF composite film decreases with increasing PMMA content, the relatively sharp diffraction peak decreases, a diffusion peak with a larger range starts to appear, and it can be seen that the relative content of the β phase in the PVDF polymer blend increases with the addition of PMMA, since the β phase of PVDF is a polar phase, the dielectric properties of the composite film increase with the increase of the content of the β phase.
FIGS. 2 to 8 are scanning electron micrographs of films prepared in comparative example 2, example 12, example 14, example 9, example 15, example 13 and comparative example 1, respectively; as can be seen from the figure, the thickness of the film prepared is about 15 μm; the PMMA and PVDF materials have good compatibility and uniform tissue structure. The PMMA/PVDF composite film has no obvious interface, smooth section, no obvious phase separation phenomenon and no obvious cracks and bubbles. The above shows that PMMA and PVDF have good compatibility and no obvious agglomeration phenomenon inside the composite film.
FIG. 9 is a graph of the dielectric properties of films prepared in examples 9, 14, 15 and comparative examples 1, 2; as can be seen from FIG. 9, also under the conditions of the heat treatment temperature of 150 ℃ and the frequency of 10Hz, the relative dielectric constant of pure PVDF is 10.1 at the maximum, the relative dielectric constant of the PMMA/PVDF composite film having the PMMA content of 50 vol% is 5.82, and the relative dielectric constant of pure PMMA is 3.98 at the minimum. The amorphous PMMA has a relatively small dielectric constant which is far lower than that of PVDF, the PMMA has a relatively low dielectric response, PVDF is diluted to a certain extent with the addition of PMMA, and the crystallinity of the copolymer is reduced in PVDF with the addition of PMMA, so that the relative dielectric constant of the PMMA/PVDF composite film is in a descending trend with the addition of PMMA. At a heat treatment temperature of 150 ℃ and a frequency of 106Under Hz, pure PVDF has the largest dielectric loss factor and pure PMMA has the smallest dielectric loss factor. This is because the dipole switching is somewhat limited by the interaction between the carbonyl groups of PMMA in the polymer and the methyl groups in the PVDF, and therefore the dielectric loss of the polymer blend is greatly reduced.
FIG. 10 is a graph showing the dielectric properties of the films prepared in examples 9, 12 and 13 and comparative examples 1 and 2. from FIG. 10, it can be seen that, also in the condition of PMMA content of 50 vol% and frequency of 10Hz, the molecular segments will absorb more energy with increasing temperature, the dipole movement speed is increased, and the interaction force between dipoles is easier to overcome under the action of the external electric field, so the dipole steering polarization strength is increased.
FIG. 11 is a Weibull plot of breakdown field strengths of films prepared in examples 9, 14, 15 and comparative examples 1, 2; as can be seen from FIG. 11, the breakdown field strength of the PMMA/PVDF composite film shows a tendency to increase and then decrease with the addition of PMMA, reaching a maximum of 590kV/mm when the content of PMMA is 50 vol%, and then to decrease with the increase of the content of PMMA. This shows that the PMMA/PVDF composite film with the blending content of 50 vol% has the function of preventing the formation of a conductive path, so that the composite film has higher breakdown bearing capacity.
FIG. 12 is a Weibull plot of breakdown field strengths of films prepared in examples 9, 12, 13 and comparative examples 1, 2; as can be seen from FIG. 12, the breakdown field strength of the PMMA/PVDF composite film obtained at the heat treatment temperature of 150 ℃ reached a maximum of 590kV/mm, and the breakdown field strength of the sample at an excessively high temperature began to decrease, which is probably due to the fact that the heat treatment temperature reached the crystalline melting point (170 ℃) of PVDF, resulting in a decrease in the breakdown performance of the sample, thus indicating that the breakdown performance of the film treated at the heat treatment temperature of 150 ℃ was optimal in this experiment.
FIG. 13 is a graph of the energy storage performance of the films prepared in examples 9, 14, 15 and comparative examples 1, 2; fig. 14 is a graph showing the energy storage properties of the thin films prepared in examples 9, 12, and 13 and comparative examples 1 and 2. Through comparison, the PMMA/PVDF composite film with the heat treatment temperature of 150 ℃ and the PMMA content of 50 vol% has higher breakdown field strength (570 kV/mm) and energy storage density (20.08J/cm)3). The molecular chain segment in the polymer is increased by the temperature to obtain more energy and the molecular polarization strengthIncreased in the number of cells. When the temperature is too high, the energy storage density decreases, which may be that the temperature reaches the crystalline melting point of PVDF (170 ℃), which has an effect on the energy storage density and the breakdown field strength. The PMMA molecules can inhibit the movement of PVDF molecular chains, so that the transmission of electrons in PVDF becomes difficult, and a conductive channel is not easily formed under the action of an external electric field, so that the breakdown field strength of the composite film is increased along with the addition of PMMA. On the other hand, PMMA has higher Young modulus, the mechanical property of the polymer is improved along with the addition of PMMA, and the puncture resistance of the polymer is enhanced. At the same time, when the content of PMMA exceeds 50 vol%, defects in the polymer increase accordingly, and the breakdown field strength of the polymer is reduced to some extent, so that when the content of PMMA is large, the breakdown field strength of the polymer begins to decrease, and the energy storage density of the polymer also decreases. Therefore, the PMMA/PVDF composite film with the heat treatment temperature of 150 ℃ and the PMMA content of 50 vol% has the best performance.

Claims (10)

1. The PMMA/PVDF composite film is characterized by being prepared by blending and hot-pressing a linear polymer PMMA and a ferroelectric polymer PVDF, wherein the volume percentage of PMMA in the composite film is 25-75 vol%.
2. A PMMA/PVDF composite film according to claim 1, wherein the PMMA is 50 vol% in the composite film.
3. A PMMA/PVDF composite film as defined in claim 2, wherein the thickness of the composite film is 10-20 μm.
4. A method for preparing a PMMA/PVDF composite film according to any one of claims 1 to 3, comprising the steps of:
preparing PMMA, DMF solution and PVDF according to a certain mass-volume ratio, adding PMMA into the DMF solution for multiple times, stirring until the mixture is clear, adding PVDF into the clear solution for multiple times, and stirring at a certain temperature to obtain a uniform colloid blended by PMMA and PVDF;
step two, stirring the blended colloid obtained in the step one under vacuum for a certain time, then carrying out vacuum pumping treatment at room temperature and standing for a certain time, blade-coating the standing blended colloid on a glass substrate by using a tape casting method, placing the glass substrate with the blended colloid under a certain temperature for heat treatment for a certain time, and removing an organic solvent to obtain a PMMA/PVDF composite membrane;
and step three, carrying out hot-pressing treatment on the PMMA/PVDF composite film obtained in the step two by adopting a hot-pressing process to obtain a compact PMMA/PVDF composite film.
5. The preparation method of the PMMA/PVDF composite film of the claim 4, characterized in that the mass-to-volume ratio of the PMMA, the DMF solution and the PVDF in the first step is (0.02-0.30) g to 1mL (0.08-0.20) g.
6. The preparation method of the PMMA/PVDF composite film as in the claim 4 or 5, characterized in that the stirring temperature in the first step is 30-70 ℃ and the stirring time is 8-15 h.
7. The preparation method of the PMMA/PVDF composite film as in claim 6, wherein the time of the vacuum stirring of the blending colloid in the second step is 2-5 h, the standing time is 8-10 h, and the vacuum degree of the vacuum stirring and vacuuming is 0.085-0.095 MPa.
8. The method for preparing PMMA/PVDF composite film according to claim 7, characterized in that the doctor blade coating speed of the casting method in the second step is 1-3 cm/s, and the doctor blade coating wet film thickness is 15-35 μm.
9. The method for preparing PMMA/PVDF composite film according to claim 8, characterized in that the heat treatment temperature of the glass substrate with the blended colloid in the second step is 60-200 ℃, and the heat treatment time is 12-20 h.
10. The method for preparing PMMA/PVDF composite film according to claim 9, characterized in that the hot pressing treatment in step three is gradient hot pressing treatment, the first stage hot pressing temperature is 90-140 ℃, and the pressure is maintained at 1-7 MPa for 20-80 min; in the second stage, pressure relief treatment is carried out, and the temperature is kept at 140-170 ℃ for 40-60 min after pressure relief so as to remove air bubbles in the composite film; the hot pressing temperature in the third stage is 140-170 ℃, and the pressure is maintained for 10-30 min under 10-20 MPa; and cooling the temperature of the PMMA/PVDF composite film to room temperature through water cooling, and maintaining the pressure for 1-5 min at 1-15 MPa.
CN201911251052.5A 2019-12-09 2019-12-09 PMMA/PVDF composite film and preparation method thereof Pending CN110951195A (en)

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US11644599B2 (en) 2020-09-25 2023-05-09 Samsung Display Co., Ltd. Cover window and display apparatus including the same
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CN113480815A (en) * 2021-08-13 2021-10-08 高亮 Polymethyl methacrylate/polyvinylidene fluoride composite material and preparation method and application thereof
CN113480815B (en) * 2021-08-13 2022-09-16 高亮 Polymethyl methacrylate/polyvinylidene fluoride composite material and preparation method and application thereof
CN114369905A (en) * 2021-12-28 2022-04-19 武汉理工大学 Polymer blend film with gradient structure and preparation method thereof
CN114369905B (en) * 2021-12-28 2023-11-07 武汉理工大学 Polymer blend film with gradient structure and preparation method thereof
CN114989464A (en) * 2022-06-02 2022-09-02 华东师范大学 PVDF/PMMA composite film and preparation method thereof
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