CN110885522B - Preparation method of PVDF (polyvinylidene fluoride) composite chitosan aerogel and induction of PVDF crystallization process - Google Patents
Preparation method of PVDF (polyvinylidene fluoride) composite chitosan aerogel and induction of PVDF crystallization process Download PDFInfo
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- CN110885522B CN110885522B CN201811055682.0A CN201811055682A CN110885522B CN 110885522 B CN110885522 B CN 110885522B CN 201811055682 A CN201811055682 A CN 201811055682A CN 110885522 B CN110885522 B CN 110885522B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
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Abstract
In the invention, a chitosan block aerogel is prepared by a freeze drying mode, PVDF is loaded in the aerogel by a dipping method to prepare a composite material with certain piezoelectricity, the loaded PVDF is found to be transformed in a crystal structure in the research process, so that the chitosan has an induction effect on the crystallization process of the PVDF, and the analysis and research are carried out on the result through SEM, FTIR and XRD.
Description
Technical Field
The invention relates to preparation of a chitosan aerogel and an induction effect of the chitosan aerogel on a polyvinylidene fluoride (PVDF) crystal form structure.
Background
Polyvinylidene fluoride (PVDF) has excellent application value in the technical field of electronic devices as an ideal piezoelectric and ferroelectric material with electromechanical conversion function, and since the piezoelectric effect in quartz crystal is discovered by Curie brother in 1880, inorganic piezoelectric materials have been the leading role in the field of piezoelectric research for a long time. In 1969, Kawai discovered in the research on polyvinylidene fluoride (PVDF), that PVDF film can be polarized by high temperature and strong electric field or stretched in single axis, and the PVDF film with strong piezoelectric effect can be obtained, since then, the organic polymer with piezoelectric property has obtained historical breakthrough, compared with the traditional inorganic piezoelectric ferroelectric material, the organic piezoelectric ferroelectric polymer has the following advantages: firstly, the chemical stability is high, and the paint is not easy to corrode and damage in severe environments such as strong acid, strong alkali and the like; secondly, the manufacturing cost is low, the mechanical elasticity is high, the processing and the forming are easy, and the application range is wide; meanwhile, the soft sensor is easy to match with the skin of a human body, and can be made into a medical sensor for checking some diseases existing in the human body; finally, the polymer film material is light, and can be processed into a large-area flexible film for producing various electromechanical transducers and array sensors.
While in the course of the study it was found that PVDF has predominantly a 4-crystal structure: alpha phase, beta phase, gamma phase and delta phase. However, not every crystal phase has piezoelectric and ferroelectric properties, but only beta and gamma phases show stronger piezoelectric and ferroelectric properties, and with the continuous development of scientific technology, a PVDF film with excellent electrical properties plays an increasingly greater role in production and life, so that the formation of the phase state and the transition between the phase states are required to be researched to obtain a high-content PVDF piezoelectric and ferroelectric phase, which has an important role in deeply understanding the influence mechanism of the structure of PVDF on the properties of PVDF.
In the invention, the chitosan block aerogel is prepared by a freeze drying mode, PVDF is loaded in the aerogel by a dipping method to prepare the composite material with certain piezoelectricity, the loaded PVDF is found to be transformed in a crystal structure in the research process, so that the chitosan has an induction effect on the crystallization process of the PVDF, and the analysis and research are carried out on the result through SEM, FTIR and XRD.
Disclosure of Invention
The invention aims to provide a preparation method of chitosan blocky aerogel and a dipping method of PVDF, and the preparation method comprises the following steps:
the method comprises the following steps: preparing the chitosan aerogel, namely putting 40 ml of deionized water into a beaker, adding a certain amount of chitosan powder under magnetic stirring, slowly adding a certain amount of acetic acid after uniformly stirring, continuously stirring at a low speed, standing for defoaming after uniformly stirring until the solution is clear.
Step two: and (3) freeze drying, pouring the solution after standing and clarification into an ampoule bottle, pre-freezing for one night at the temperature of minus 20 ℃, and then drying for 48 hours at the temperature of minus 90 ℃ in a vacuum environment to prepare the chitosan block aerogel.
Step three: 20 ml of N-N dimethylformamide is put into a beaker, a certain amount of PVDF powder is added, the mixture is stirred for 8 hours and is subjected to ultrasonic treatment for 3 hours before use, and then a clear PVDF solution is prepared.
Step four: and (3) putting the prepared chitosan block aerogel into a clear PVDF solution to ensure that the chitosan block aerogel is completely immersed into the solution, and sealing and standing the preservative film for 24 hours.
Step five: and (3) placing the impregnated sample in a vacuum drying oven, and drying at 50 ℃ for 4 h to prepare the PVDF/chitosan aerogel composite material.
The further preferable scheme of the invention is as follows: in the preparation stage of the chitosan aerogel, the sample with the continuous stirring time of more than 12 hours is more uniform.
The further preferable scheme of the invention is as follows: the amount of chitosan is 2-1 g, and the sample can be damaged if the amount of chitosan is excessive or small.
The further preferable scheme of the invention is as follows: the amount of acetic acid is about 2% of the volume of the solution, and the excessive amount can cause the precipitation of chitosan.
The further preferable scheme of the invention is as follows: the impregnation amount of the PVDF is about 10-20% of the mass fraction of the composite material.
In the invention, the chitosan block aerogel is prepared by a freeze drying mode, PVDF is loaded in the aerogel by a dipping method to prepare the composite material with certain piezoelectricity, the loaded PVDF is found to be transformed in a crystal structure in the research process, so that the chitosan has an induction effect on the crystallization process of the PVDF, and the analysis and research are carried out on the result through SEM, FTIR and XRD.
Drawings
FIG. 1 is a macroscopic photograph of composite materials of different loading concentrations of PVDF prepared by the present invention;
FIG. 2 is a microscopic photograph of a PVDF-loaded chitosan aerogel prepared by the present invention;
FIG. 3 is the mechanical properties of the PVDF aerogels obtained by the preparation method of the invention with different loading concentrations;
FIG. 4 is an XRD pattern of PVDF composites of different loading concentrations obtained from the preparation of the present invention;
FIG. 5 is a FTIR plot of different loading concentrations of PVDF composites obtained in the preparation of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
And (2) putting 40 ml of deionized water into a beaker, adding 1 g of chitosan powder under magnetic stirring, slowly adding 0.8 ml of acetic acid after uniform stirring, continuously stirring at a low speed, standing for defoaming after uniform stirring until the solution is clear, pouring the solution after standing for clarification into an ampoule bottle, pre-freezing for one night at-20 ℃, and then drying for 48 hours at-90 ℃ under a vacuum environment to prepare the chitosan block aerogel.
Adding 1.58g of PVDF powder into 20 ml of N-N dimethylformamide in a beaker, stirring for 8 hours, performing ultrasonic treatment for 3 hours before use to prepare a clear PVDF solution, putting the prepared chitosan block aerogel into the clear PVDF solution to ensure that the chitosan block aerogel is completely immersed in the solution, sealing and standing the preservative film for 24 hours, putting the soaked sample in a vacuum drying oven, and drying at 50 ℃ for 4 hours. And preparing the PVDF/chitosan aerogel composite material.
Example 2
And (2) putting 40 ml of deionized water into a beaker, adding 1.5 g of chitosan powder under magnetic stirring, slowly adding 0.8 ml of acetic acid after uniformly stirring, continuously stirring at a low speed, standing for defoaming after uniformly stirring until the solution is clear, pouring the solution after standing for clarification into an ampoule bottle, pre-freezing for one night at-20 ℃, and then drying for 48 hours at-90 ℃ under a vacuum environment to prepare the chitosan block aerogel.
Adding 1.58g of PVDF powder into 20 ml of N-N dimethylformamide in a beaker, stirring for 8 hours, performing ultrasonic treatment for 3 hours before use to prepare a clear PVDF solution, putting the prepared chitosan block aerogel into the clear PVDF solution to ensure that the chitosan block aerogel is completely immersed in the solution, sealing and standing the preservative film for 24 hours, putting the soaked sample in a vacuum drying oven, and drying at 50 ℃ for 4 hours. And preparing the PVDF/chitosan aerogel composite material.
Example 3
And (2) putting 40 ml of deionized water into a beaker, adding 2 g of chitosan powder under magnetic stirring, slowly adding 0.8 ml of acetic acid after uniformly stirring, continuously stirring at a low speed, standing for defoaming after uniformly stirring until the solution is clear, pouring the solution after standing for clarification into an ampoule bottle, pre-freezing for one night at-20 ℃, and then drying for 48 hours at-90 ℃ under a vacuum environment to prepare the chitosan block aerogel.
Adding 1.58g of PVDF powder into 20 ml of N-N dimethylformamide in a beaker, stirring for 8 hours, performing ultrasonic treatment for 3 hours before use to prepare a clear PVDF solution, putting the prepared chitosan block aerogel into the clear PVDF solution to ensure that the chitosan block aerogel is completely immersed in the solution, sealing and standing the preservative film for 24 hours, putting the soaked sample in a vacuum drying oven, and drying at 50 ℃ for 4 hours. And preparing the PVDF/chitosan aerogel composite material.
Example 4
And (2) putting 40 ml of deionized water into a beaker, adding 1 g of chitosan powder under magnetic stirring, slowly adding 0.8 ml of acetic acid after uniform stirring, continuously stirring at a low speed, standing for defoaming after uniform stirring until the solution is clear, pouring the solution after standing for clarification into an ampoule bottle, pre-freezing for one night at-20 ℃, and then drying for 48 hours at-90 ℃ under a vacuum environment to prepare the chitosan block aerogel.
20 ml of N-N dimethylformamide is taken in a beaker, 2.27g of PVDF powder is added, the mixture is stirred for 8 hours and is sonicated for 3 hours before use. Preparing a clear PVDF solution, putting the prepared chitosan block aerogel into the clear PVDF solution to ensure that the chitosan block aerogel is completely immersed in the solution, sealing a preservative film, standing for 24 hours, putting a sample after the soaking in a vacuum drying oven, and drying for 4 hours at 50 ℃ to prepare the PVDF/chitosan aerogel composite material.
Example 5
And (2) putting 40 ml of deionized water into a beaker, adding 1.5 g of chitosan powder under magnetic stirring, slowly adding 0.8 ml of acetic acid after uniformly stirring, continuously stirring at a low speed, standing for defoaming after uniformly stirring until the solution is clear, pouring the solution after standing for clarification into an ampoule bottle, pre-freezing for one night at-20 ℃, and then drying for 48 hours at-90 ℃ under a vacuum environment to prepare the chitosan block aerogel.
Adding 20 ml of N-N dimethylformamide into a beaker, adding 2.27g of PVDF powder, stirring for 8 hours, performing ultrasonic treatment for 3 hours before use to prepare a clear PVDF solution, putting the prepared chitosan block aerogel into the clear PVDF solution to ensure that the chitosan block aerogel is completely immersed into the solution, sealing a preservative film, standing for 24 hours, putting the soaked sample into a vacuum drying oven, and drying for 4 hours at 50 ℃. And preparing the PVDF/chitosan aerogel composite material.
Example 6
And (2) putting 40 ml of deionized water into a beaker, adding 2 g of chitosan powder under magnetic stirring, slowly adding 0.8 ml of acetic acid after uniformly stirring, continuously stirring at a low speed, standing for defoaming after uniformly stirring until the solution is clear, pouring the solution after standing for clarification into an ampoule bottle, pre-freezing for one night at-20 ℃, and then drying for 48 hours at-90 ℃ under a vacuum environment to prepare the chitosan block aerogel.
Adding 20 ml of N-N dimethylformamide into a beaker, adding 2.27g of PVDF powder, stirring for 8 hours, performing ultrasonic treatment for 3 hours before use to prepare a clear PVDF solution, putting the prepared chitosan block aerogel into the clear PVDF solution to ensure that the chitosan block aerogel is completely immersed into the solution, sealing a preservative film, standing for 24 hours, putting the soaked sample into a vacuum drying oven, and drying at 50 ℃ for 4 hours to prepare the PVDF/chitosan aerogel composite material.
Claims (1)
1. A preparation method of a PVDF composite chitosan aerogel comprises the following steps:
the method comprises the following steps: preparing chitosan aerogel, namely putting 40 ml of deionized water into a beaker, adding 1-3 g of chitosan powder under magnetic stirring, slowly adding 2% of acetic acid relative to the volume fraction of the deionized water after uniformly stirring, continuously stirring at a low speed, standing for defoaming after uniformly stirring until the solution is clear;
step two: freeze drying, pouring the settled and clarified solution into an ampoule bottle, pre-freezing for one night at-20 ℃, and then drying for 48 hours at-90 ℃ under a vacuum environment to prepare the chitosan block aerogel;
step three: adding 20 ml of N-N dimethylformamide into a beaker, adding a certain amount of PVDF powder, stirring for 8 hours, and performing ultrasonic treatment for 3 hours before use to prepare a clear PVDF solution;
step four: putting the prepared chitosan block aerogel into a clear PVDF solution to ensure that the chitosan block aerogel is completely immersed in the solution, and sealing and standing the preservative film for 24 hours;
step five: and (3) placing the impregnated sample in a vacuum drying oven, and drying at 50 ℃ for 4 h to prepare the PVDF/chitosan aerogel composite material, wherein the impregnated amount of the PVDF accounts for 10-20% of the mass fraction of the composite material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977524A (en) * | 2012-06-30 | 2013-03-20 | 杭州师范大学 | Polyvinylidene fluoride composite material and preparation method thereof |
| US20180040806A1 (en) * | 2016-08-05 | 2018-02-08 | Wisconsin Alumni Research Foundation | Flexible compact nanogenerators based on mechanoradical-forming porous polymer films |
| CN108285549A (en) * | 2017-01-17 | 2018-07-17 | 武汉力诚生物科技有限公司 | A kind of plant polyose insulation aerogel material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4832739B2 (en) * | 2004-08-24 | 2011-12-07 | 株式会社クレハ | Method for producing vinylidene fluoride resin porous membrane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977524A (en) * | 2012-06-30 | 2013-03-20 | 杭州师范大学 | Polyvinylidene fluoride composite material and preparation method thereof |
| US20180040806A1 (en) * | 2016-08-05 | 2018-02-08 | Wisconsin Alumni Research Foundation | Flexible compact nanogenerators based on mechanoradical-forming porous polymer films |
| CN108285549A (en) * | 2017-01-17 | 2018-07-17 | 武汉力诚生物科技有限公司 | A kind of plant polyose insulation aerogel material and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| A novel Cd2+-imprinted chitosan-based composite membrane for Cd2+ removal from aqueous solution;Xuejiao Tang et al;《Materials Letters》;20170404;第121-123页 * |
| 不同干燥条件下聚偏氟乙烯的结晶与电池性能;张翠芬 等;《电池》;20020831;第32卷(第4期);第211-213页 * |
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