CN110776703A - Blend with self-repairing performance, blend film, preparation method and application thereof - Google Patents

Blend with self-repairing performance, blend film, preparation method and application thereof Download PDF

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CN110776703A
CN110776703A CN201810852611.7A CN201810852611A CN110776703A CN 110776703 A CN110776703 A CN 110776703A CN 201810852611 A CN201810852611 A CN 201810852611A CN 110776703 A CN110776703 A CN 110776703A
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李瑀
梁子嘉
曹晨
封伟
冯奕钰
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Tianjin University
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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Abstract

The invention discloses a blend with self-repairing performance, a blend film, a preparation method and application thereof, in particular to a self-repairing material formed by the hydrogen bond action of amide gel and the dynamic covalent bond action of borax, a preparation process and application thereof as capacitor electrolyte; taking azodiisobutyronitrile as an initiator, obtaining an alternating polymer of vinyl benzenesulfonylimine lithium salt and maleic anhydride in a free radical polymerization mode, preparing a self-repairing polymer by a Leibler method, blending the vinyl benzenesulfonylimine lithium salt and the maleic anhydride, adding borax, and preparing the electrolyte film by a tape casting method.

Description

Blend with self-repairing performance, blend film, preparation method and application thereof
Technical Field
The invention relates to the technical field of material chemistry, in particular to a blend with self-repairing performance, a blend film, a preparation method and application thereof.
Background
As the three major industries in the 21 st century, energy plays an indispensable role in life and production. In the face of increasing energy demand, besides popularizing the original energy technology and developing new equipment to improve the utilization efficiency of energy, the vigorous development and attention on new energy and renewable energy also become an indispensable topic. Therefore, development of portable energy devices and intelligent energy storage devices and development of green energy devices such as capacitors with good energy density, cycling stability and charge and discharge performance are needed in the social energy field.
In a portable energy device and an intelligent energy storage device, a capacitor is considered as an important novel energy device, in real life, the capacitor is more and more widely applied, and the capacitor is used and researched in energy storage devices of mobile phones, automobiles and large-scale equipment. In the research field, the capacitor can be divided into two parts, namely an electrode and an electrolyte, according to the structure of the capacitor. As for the electrolyte, the conventional liquid electrolyte has disadvantages such as leakage and flammability, and researchers hope to change it into a polymer electrolyte to improve its performance. The traditional polymer electrolyte is formed by compounding a polymer serving as a matrix and lithium salt ions. Is considered to be an excellent substitute for the conventional liquid electrolyte due to its good thermal stability and no leakage of the liquid organic electrolyte. However, the polymer electrolyte after being improved also has a problem of being easily damaged by a machine compared to a liquid electrolyte, and thus self-repairing ability of the electrolyte is included in the research field, so that it is expected to develop a flexible wearable electronic product and impart excellent resistance to mechanical abrasion.
The intelligent electrochemical energy storage device is a new generation of energy storage and conversion equipment with self-repairing capability or shape memory capability represented by an intelligent super capacitor and an intelligent capacitor, and the development of the device benefits from the research progress of self-repairing high molecular materials, self-repairing conductive materials and shape memory materials in material science. Generally, the intelligent self-repairing electrochemical energy storage device is provided with an electrode material capable of self-repairing or an electrolyte material capable of self-repairing or both, and the flexible structure and the repairing characteristic of the device provide good conditions for wide application of wearable electronic equipment. The self-repairing capability is taken as a special performance of the material, and is generally realized through reversible dynamic covalent bonds and non-covalent bonds, such as hydrogen bonds, van der waals force, ion coupling effect and the like, when the material is damaged from the outside, new bonding effect is formed again through reversible bonding between molecules, and the self-repairing performance of the material is realized. The self-repairing materials in the current research stage are usually completed through a self-repairing mechanism, and the self-repairing materials are rarely used in electrolytes.
Disclosure of Invention
The invention aims to provide a blend with self-repairing performance, a blend film, a preparation method and application thereof aiming at the technical defects in the prior art, and the blend film jointly realize the rapid self-repairing of an electrolyte through two self-repairing mechanisms, namely through the hydrogen bond action between amide bonds and the dynamic covalent bond of a dynamic boron ester bond.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a blend with self-repairing performance is prepared by blending styryl bissulfonyl imide lithium salt with alternating polymer P of maleic anhydride, self-repairing polymer of amides and borax, and the obtained blend realizes intrinsic self-repairing through two interactions of dynamic boron ester bond and hydrogen bond, wherein:
the structural formula of the alternating polymer P is as follows:
Figure BDA0001747809370000021
the structural formula of the self-repairing polymer is as follows:
Figure BDA0001747809370000022
in the above technical scheme, the blend is prepared according to the following method:
dissolving the alternating polymer P and the self-repairing polymer in DMSO according to a mass ratio of 1 (1-3), heating and stirring for 10-15h at 50-70 ℃ to obtain a mixed solution, and adding an aqueous solution of borax into the system in the solution cooling process, wherein the volume ratio of the mixed solution to the aqueous solution of borax is 9:1, and the concentration of the aqueous solution of borax is 1mM-5mM to obtain a blend.
In the above technical scheme, the mass ratio of the alternating polymer P to the self-repairing polymer is 1: 2.
A blend film having self-healing properties prepared by the process of: and (3) dropwise adding the blend onto a clean glass plate through a filter gauze, and drying for 15-30h at 70-90 ℃ in a vacuum environment to obtain the blend membrane.
In the above technical solution, the preparation method of the alternating polymer P comprises the following steps:
according to a molar ratio of 1: adding lithium salt monomer STSSSILi and maleic anhydride into dimethyl sulfoxide (DMSO) to dissolve, then adding Azobisisobutyronitrile (AIBN), wherein the molar ratio of AIBN to lithium salt monomer STSSSILi is 0.004:1, obtaining a reaction system, placing the reaction system into liquid nitrogen to cool and vacuumize, reacting at 50-70 ℃ for 40-60h under a vacuum condition, exposing the reaction system to air after the reaction is finished, then precipitating polymer DMSO solution into tetrahydrofuran, purifying, and precipitating for three times to remove unreacted monomers.
In the above technical scheme, the preparation method of the self-repairing polymer comprises the following steps:
mixing diacid-triacid mixture (DM-85) and Diethylenetriamine (DETA) according to the molar ratio of 1:1, reacting for 10-15h at the temperature of 120-180 ℃ under the protection of nitrogen, dissolving the obtained product in chloroform under heating, then cooling to room temperature, extracting for 2-4 times by deionized water, concentrating, adding urea, wherein the molar ratio of the urea to the diethylenetriamine is (0.2-0.3):1, and reacting for 4-6h in argon at the temperature of 130-150 ℃ to synthesize the self-repairing polymer.
In another aspect of the invention, the application of the blend film with the self-repairing performance in the super capacitor is also included.
In another aspect of the present invention, a method for preparing a blend film having self-repairing properties, comprises the steps of:
step 1, dissolving an alternating polymer P and the self-repairing polymer in DMSO according to a mass ratio of 1 (1-3), heating and stirring for 10-15h at 50-70 ℃ to obtain a mixed solution, and adding a borax aqueous solution into a system in a solution cooling process, wherein the volume ratio of the mixed solution to the borax aqueous solution is 9:1, and the concentration of the borax aqueous solution is 1mM-5mM to obtain a mixed system;
and 2, dropwise adding the blend onto a clean glass plate through a filter gauze, and drying for 15-30h at 70-90 ℃ in a vacuum environment to obtain the blend membrane.
In the technical scheme, the preparation method of the alternating polymer P comprises the following steps,
according to a molar ratio of 1:1 adding lithium salt monomer STSSSILi and maleic anhydride into dimethyl sulfoxide DMSO for dissolving, then adding azodiisobutyronitrile AIBN, wherein the molar ratio of AIBN to lithium salt monomer STSSSILi is 0.004:1, obtaining a reaction system, placing the reaction system into liquid nitrogen for cooling and vacuumizing, reacting for 40-60h at 50-70 ℃ under a vacuum condition, exposing the reaction system to air after the reaction is finished, then precipitating a polymer DMSO solution into tetrahydrofuran, purifying, and precipitating for three times to remove unreacted monomers.
In the technical scheme, the preparation method of the self-repairing polymer comprises the following steps,
mixing diacid-triacid mixture (DM-85) and Diethylenetriamine (DETA) according to the molar ratio of 1:1, reacting for 10-15h at the temperature of 120-180 ℃ under the protection of nitrogen, dissolving the obtained product in chloroform under heating, then cooling to room temperature, extracting for 2-4 times by deionized water, concentrating, adding urea, wherein the molar ratio of the urea to the diethylenetriamine is (0.2-0.3):1, and reacting for 4-6h in argon at the temperature of 130-150 ℃ to synthesize the self-repairing polymer.
Compared with the prior art, the invention has the beneficial effects that:
1. the electrolyte film obtained by the steps has good self-repairing capability and is reflected in SEM pictures. And after the self-repairing is carried out for many times, a part of the original electrochemical performance can still be maintained.
2. The intrinsic self-repairing of the material is realized through two interactions of the dynamic boron ester bond and the hydrogen bond. Provides a novel thought for the research of self-repairing materials and also provides a feasible scheme for the self-repairing field of electrolytes.
Drawings
FIG. 1 is a scanning electron micrograph of the resulting blended material of example 3;
FIG. 2 is an optical microscopic representation before failure and after self-repair for 10min, wherein a is the optical microscopic representation of the surface of example 1; b is the characterization picture of the optical microscope after the surface cutting of example 1; c is a representation of an optical microscope after self-repairing for 10min in example 1; d is the characterization of the optical microscope after self-repairing for 10min of example 5.
FIG. 3 is a graph comparing the cyclic voltammograms of the materials obtained in examples 1-5 before cutting and after self-healing;
FIG. 4 is an infrared characterization of alternating polymer P.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
1) Preparation of alternating Polymer P of lithium salt of styryl bis-sulfonylimide and maleic anhydride (STSSSILi-alt-MA)
According to a molar ratio of 1: lithium salt monomer STSSSILi and Maleic Anhydride (MA) are poured into a polymerization tube, and then dimethyl sulfoxide (DMSO) is added to dissolve the lithium salt monomer STSSSILi and maleic anhydride, and then 0.1% (molar ratio) of Azobisisobutyronitrile (AIBN) is added. And (3) putting the polymerization tube into liquid nitrogen for cooling, introducing nitrogen, vacuumizing for three times, sealing the tube by using an alcohol blast burner, and putting the tube into an oil bath kettle at the temperature of 60 ℃ for reacting for 48 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. Then, the polymer solution in DMSO is precipitated in tetrahydrofuran, and purification treatment is carried out, and precipitation is carried out three times to remove unreacted monomers.
The structural formula of the lithium salt monomer STSSSILi is as follows:
the reaction principle is described in Lizhen Long, Shuanjin Wang, et al, polymers for lithium polymers [ J ]. Journal of Materials chemistry A,2016,4: 10038-.
2) Preparation of self-repairing polymer
The diacid-triacid mixture (DM-85) and the Diethylenetriamine (DETA) react for 12 hours at 160 ℃ under the protection of nitrogen atmosphere under the action of mechanical stirring according to the molar ratio of 1: 1. The resulting product was dissolved in chloroform under heating. After cooling to room temperature, it was extracted three times with deionized water and then concentrated by rotary evaporation. Adding 0.25mol of urea to react with the product, and reacting for 5 hours at 140 ℃ in argon to synthesize the self-repairing polymer.
The diacid in DM-85 is p-phenylenediacetic acid and o-phenylenediacetic acid, the triacid is 1,2, 4-triphenylacetic acid, and DM-85 is a proportional relation.
The reaction procedure is described in detail in the references Yang ZHao, Ye ZHang, Hao Sun, et al.A Self-healing aqueous Lithium-Ion Battery [ J ]. Angewandte Chemie,2016,55:1-6.
3) Blending of self-healing polymers with alternating polymers P
Dissolving the alternating polymer P and the self-repairing polymer in DMSO according to the mass percentage of 1:1, heating and stirring for 12h at 60 ℃, adding 1mM borax solution into the system in the solution cooling process, and dripping the borax solution on a pre-cleaned glass slide by a tape casting method to form a blend film.
Example 2
1) Preparation of alternating Polymer P of lithium salt of styryl bis-sulfonylimide and maleic anhydride (STSSSILi-alt-MA)
According to a molar ratio of 1: lithium salt monomer STSSSILi and Maleic Anhydride (MA) are poured into a polymerization tube, and then dimethyl sulfoxide (DMSO) is added to dissolve the lithium salt monomer STSSSILi and maleic anhydride, and then 0.2% (molar ratio) of Azobisisobutyronitrile (AIBN) is added. And (3) putting the polymerization tube into liquid nitrogen for cooling, introducing nitrogen, vacuumizing for three times, sealing the tube by using an alcohol blast burner, and putting the tube into an oil bath kettle at the temperature of 60 ℃ for reacting for 48 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. Then, the polymer solution in DMSO is precipitated in tetrahydrofuran, and purification treatment is carried out, and precipitation is carried out three times to remove unreacted monomers.
2) Preparation of self-repairing polymer
The diacid-triacid mixture (DM-85) and the Diethylenetriamine (DETA) react for 12 hours at 160 ℃ under the protection of nitrogen atmosphere under the action of mechanical stirring according to the molar ratio of 1: 1. The resulting product was dissolved in chloroform under heating. After cooling to room temperature, it was extracted three times with deionized water and then concentrated by rotary evaporation. Adding 0.25mol of urea to react with the product, and reacting for 5 hours at 140 ℃ in argon to synthesize the self-repairing polymer.
3) Blending of self-healing polymers with alternating polymers P
Dissolving the alternating polymer P and the self-repairing polymer in DMSO according to the mass percentage of 2:3, heating and stirring for 12h at 60 ℃, adding 2mM borax solution into the system in the solution cooling process, and dripping the borax solution onto a pre-cleaned glass slide and a blend film by a tape casting method.
Example 3
1) Preparation of styrene-based bissulfonylimide lithium salt and maleic anhydride alternating polymer P (STSSILI-alt-MA)
According to a molar ratio of 1: lithium salt monomer STSSSILi and Maleic Anhydride (MA) are poured into a polymerization tube, and then dimethyl sulfoxide (DMSO) is added to dissolve the lithium salt monomer STSSSILi and maleic anhydride, and then 0.3% (molar ratio) of Azobisisobutyronitrile (AIBN) is added. And (3) putting the polymerization tube into liquid nitrogen for cooling, introducing nitrogen, vacuumizing for three times, sealing the tube by using an alcohol blast burner, and putting the tube into an oil bath kettle at the temperature of 60 ℃ for reacting for 48 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. Then, the polymer solution in DMSO is precipitated in tetrahydrofuran, and purification treatment is carried out, and precipitation is carried out three times to remove unreacted monomers.
2) Preparation of self-repairing polymer
The diacid-triacid mixture (DM-85) and the Diethylenetriamine (DETA) react for 12 hours at 160 ℃ under the protection of nitrogen atmosphere under the action of mechanical stirring according to the molar ratio of 1: 1. The resulting product was dissolved in chloroform under heating. After cooling to room temperature, it was extracted three times with deionized water and then concentrated by rotary evaporation. Adding 0.25mol of urea to react with the product, and reacting for 5 hours at 140 ℃ in argon to synthesize the self-repairing polymer.
3) Blending of self-healing polymers with alternating polymers P
Dissolving the alternating polymer P and the self-repairing polymer in DMSO according to the mass percentage of 1:2, heating and stirring for 12h at 60 ℃, adding 3mM borax solution into the system in the solution cooling process, and dripping the borax solution onto a pre-cleaned glass slide and a blend film by a tape casting method.
Example 4
1) Preparation of styrene-based bissulfonylimide lithium salt and maleic anhydride alternating polymer P (STSSILI-alt-MA)
According to a molar ratio of 1: lithium salt monomer STSSSILi and Maleic Anhydride (MA) are poured into a polymerization tube, and then dimethyl sulfoxide (DMSO) is added to dissolve the lithium salt monomer STSSSILi and maleic anhydride, and then 0.4% (molar ratio) of Azobisisobutyronitrile (AIBN) is added. And (3) putting the polymerization tube into liquid nitrogen for cooling, introducing nitrogen, vacuumizing for three times, sealing the tube by using an alcohol blast burner, and putting the tube into an oil bath kettle at the temperature of 60 ℃ for reacting for 48 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. Then, the polymer solution in DMSO is precipitated in tetrahydrofuran, and purification treatment is carried out, and precipitation is carried out three times to remove unreacted monomers.
2) Preparation of self-repairing polymer
The diacid-triacid mixture (DM-85) and the Diethylenetriamine (DETA) react for 12 hours at 160 ℃ under the protection of nitrogen atmosphere under the action of mechanical stirring according to the molar ratio of 1: 1. The resulting product was dissolved in chloroform under heating. After cooling to room temperature, it was extracted three times with deionized water and then concentrated by rotary evaporation. Adding 0.25mol of urea to react with the product, and reacting for 5 hours at 140 ℃ in argon to synthesize the self-repairing polymer.
3) Blending of self-healing polymers with alternating polymers P
Dissolving the alternating polymer P and the self-repairing polymer in DMSO according to the mass percentage of 2:5, heating and stirring for 12h at 60 ℃, adding a 4mM borax solution into the system in the solution cooling process, and dripping the borax solution onto a pre-cleaned glass slide and a blend film by a tape casting method.
Example 5
1) Preparation of styrene-based bissulfonylimide lithium salt and maleic anhydride alternating polymer P (STSSILI-alt-MA)
According to a molar ratio of 1: lithium salt monomer STSSSILi and Maleic Anhydride (MA) are poured into a polymerization tube, and then dimethyl sulfoxide (DMSO) is added to dissolve the lithium salt monomer STSSSILi and maleic anhydride, and then 0.5% (molar ratio) of Azobisisobutyronitrile (AIBN) is added. And (3) putting the polymerization tube into liquid nitrogen for cooling, introducing nitrogen, vacuumizing for three times, sealing the tube by using an alcohol blast burner, and putting the tube into an oil bath kettle at the temperature of 60 ℃ for reacting for 48 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. Then, the polymer solution in DMSO is precipitated in tetrahydrofuran, and purification treatment is carried out, and precipitation is carried out three times to remove unreacted monomers.
2) Preparation of self-repairing polymer
The diacid-triacid mixture (DM-85) and the Diethylenetriamine (DETA) react for 12 hours at 160 ℃ under the protection of nitrogen atmosphere under the action of mechanical stirring according to the molar ratio of 1: 1. The resulting product was dissolved in chloroform under heating. After cooling to room temperature, it was extracted three times with deionized water and then concentrated by rotary evaporation. Adding 0.25mol of urea to react with the product, and reacting for 5 hours at 140 ℃ in argon to synthesize the self-repairing polymer.
3) Blending of self-healing polymers with alternating polymers P
Dissolving the alternating polymer P and the self-repairing polymer in DMSO according to the mass percentage of 1:3, heating and stirring for 12h at 60 ℃, adding 5mM borax solution into the system in the solution cooling process, and dripping the borax solution onto a pre-cleaned glass slide and a blend film by a tape casting method.
FIG. 1 is a scanning electron micrograph of the material obtained under example 3. In the first figure, it can be seen that the material was cut to produce a scratch of 70 μm, and after being left at room temperature for 15min, the scratch was observed to become small and to become 30 μm, thereby demonstrating the self-repairing property of the material.
FIG. 2 is an optical microscopic representation before failure and after self-repair for 10min, wherein a is the optical microscopic representation of the surface of example 1; b is the characterization picture of the optical microscope after the surface cutting of example 1; c is a representation of an optical microscope after self-repairing for 10min in example 1; d is the characterization of the optical microscope after self-repairing for 10min of example 5. As can be seen from comparison in the figure, scratches are obviously generated on the surface of the cut material, and after 10min, the scratches on the surface of the material in different examples (with different borax concentrations) are reduced, so that the self-repairing performance is embodied, but the self-repairing effect is slightly different.
FIG. 3 is a comparison of cyclic voltammograms before failure of example 1 and after self-repair of the sets of example materials after failure. As can be seen from the figure, the electrochemical performance of the material before being damaged is good, the measurement curve is very close to an ideal rectangle, and the electrochemical performance of each group of examples after being damaged is slightly reduced, but the materials still have a better capacitance. The material has self-repairing performance which can meet the use requirement to a certain extent, and can still maintain electrochemical performance at a certain level under the condition of external mechanical damage.
FIG. 4 is an infrared characterization of the lithium salt of styryl bissulfonylimide and alternating polymer of maleic anhydride P (STSSSILi-alt-MA) portion of the preparation of the blended material. As can be seen, two strong peaks around 1330cm-1 and 1140cm-1 demonstrate the presence of sulfonyl groups in the polymer; the characteristic absorption peaks near 1780cm-1 and 1850cm correspond to the stretching vibration peaks caused by the symmetry and antisymmetry of the C ═ O bond on maleic anhydride, which proves that maleic anhydride and lithium styryl bissulfonylimide are well copolymerized together.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The blend with self-repairing performance is characterized by being formed by blending styrene-based bissulfonyl imide lithium salt, alternating polymer P of maleic anhydride, self-repairing polymer of amides and borax, and the obtained blend realizes intrinsic self-repairing through two interactions of dynamic boron ester bonds and hydrogen bonds, wherein:
the structural formula of the alternating polymer P is as follows:
Figure FDA0001747809360000011
the structural formula of the self-repairing polymer is as follows:
Figure FDA0001747809360000012
2. the blend of claim 1, wherein the mass ratio of the alternating polymer P to the self-healing polymer is 1: 2.
3. The blend of claim 1, wherein the blend is prepared according to the following process:
dissolving the alternating polymer P and the self-repairing polymer in DMSO according to a mass ratio of 1 (1-3), heating and stirring for 10-15h at 50-70 ℃ to obtain a mixed solution, and adding a borax aqueous solution into the system in the solution cooling process, wherein the volume ratio of the mixed solution to the borax aqueous solution is 9:1, and the concentration of the borax aqueous solution is 1-5mM to obtain a blend.
4. The blend according to claim 1, characterized in that the process for the preparation of said alternating polymers P comprises the following steps:
according to a molar ratio of 1:1 adding lithium salt monomer STSSSILi and maleic anhydride into dimethyl sulfoxide DMSO for dissolving, then adding azodiisobutyronitrile AIBN, wherein the molar ratio of AIBN to lithium salt monomer STSSSILi is 0.004:1, obtaining a reaction system, placing the reaction system into liquid nitrogen for cooling and vacuumizing, reacting for 40-60h at 50-70 ℃ under a vacuum condition, exposing the reaction system to air after the reaction is finished, then precipitating a polymer DMSO solution into tetrahydrofuran, purifying, and precipitating for three times to remove unreacted monomers.
5. The blend of claim 1, wherein the process for preparing the self-healing polymer comprises the steps of:
mixing diacid-triacid mixture (DM-85) and Diethylenetriamine (DETA) according to the molar ratio of 1:1, reacting for 10-15h at the temperature of 120-180 ℃ under the protection of nitrogen, dissolving the obtained product in chloroform under heating, then cooling to room temperature, extracting for 2-4 times by deionized water, concentrating, adding urea, wherein the molar ratio of the urea to the diethylenetriamine is (0.2-0.3):1, and reacting for 4-6h in argon at the temperature of 130-150 ℃ to synthesize the self-repairing polymer.
6. A blend film having self-healing properties, prepared by the method of: dropping the blend of any of claims 1-5 through a filter gauze onto a clean glass plate, and drying at 70-90 ℃ for 15-30h in a vacuum environment to obtain a blend film.
7. Use of the blend film of self-healing properties according to claim 6 as electrolyte film in supercapacitors.
8. A preparation method of a blend film with self-repairing performance is characterized by comprising the following steps:
step 1, dissolving an alternating polymer P and the self-repairing polymer in DMSO according to a mass ratio of 1 (1-3), heating and stirring for 10-15h at 50-70 ℃ to obtain a mixed solution, and adding a borax aqueous solution into a system in a solution cooling process, wherein the volume ratio of the mixed solution to the borax aqueous solution is 9:1, and the concentration of the borax aqueous solution is 1mM-5mM to obtain a mixed system;
and 2, dropwise adding the blend onto a clean glass plate through a filter gauze, and drying for 15-30h at 70-90 ℃ in a vacuum environment to obtain the blend membrane.
9. The process according to claim 8, wherein the process for preparing the alternating polymer P comprises the steps of,
according to a molar ratio of 1:1 adding lithium salt monomer STSSSILi and maleic anhydride into dimethyl sulfoxide DMSO for dissolving, then adding azodiisobutyronitrile AIBN, wherein the molar ratio of AIBN to lithium salt monomer STSSSILi is 0.004:1, obtaining a reaction system, placing the reaction system into liquid nitrogen for cooling and vacuumizing, reacting for 40-60h at 50-70 ℃ under a vacuum condition, exposing the reaction system to air after the reaction is finished, then precipitating a polymer DMSO solution into tetrahydrofuran, purifying, and precipitating for three times to remove unreacted monomers.
10. The method of manufacturing of claim 8, wherein the method of manufacturing the self-healing polymer comprises the steps of,
mixing diacid-triacid mixture (DM-85) and Diethylenetriamine (DETA) according to the molar ratio of 1:1, reacting for 10-15h at the temperature of 120-180 ℃ under the protection of nitrogen, dissolving the obtained product in chloroform under heating, then cooling to room temperature, extracting for 2-4 times by deionized water, concentrating, adding urea, wherein the molar ratio of the urea to the diethylenetriamine is (0.2-0.3):1, and reacting for 4-6h in argon at the temperature of 130-150 ℃ to synthesize the self-repairing polymer.
CN201810852611.7A 2018-07-30 2018-07-30 Blend with self-repairing performance, blend film, preparation method and application thereof Pending CN110776703A (en)

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