WO2022016713A1 - 一种可自愈合气凝胶 - Google Patents

一种可自愈合气凝胶 Download PDF

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WO2022016713A1
WO2022016713A1 PCT/CN2020/122319 CN2020122319W WO2022016713A1 WO 2022016713 A1 WO2022016713 A1 WO 2022016713A1 CN 2020122319 W CN2020122319 W CN 2020122319W WO 2022016713 A1 WO2022016713 A1 WO 2022016713A1
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healing
self
aerogel
solution
aqueous solution
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French (fr)
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陈少军
谢家朋
王彩
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Shenzhen University
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/048—Elimination of a frozen liquid phase
    • C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2329/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Definitions

  • the invention relates to the field of aerogel, in particular to a self-healing aerogel.
  • Aerogel also known as xerogel, is a form of solid matter and is the least dense solid, about 3 kilograms per cubic meter.
  • the common aerogel is silicon aerogel.
  • aerogels There are many types of aerogels, including silicon series, carbon series, sulfur series, metal oxide series, metal series, etc., as long as the gel of any substance can be dried to remove the interior After the solvent is removed, its shape can be basically kept unchanged, and the product has high porosity and low density, which can be called aerogel.
  • aerogel As a nanoporous material with controllable structure, aerogel has unique advantages such as high specific surface area, tunable pore size, tunable framework and special surface properties. Applications in many high-tech fields such as electrodes and biotechnology have also received more and more attention.
  • aerogels have an arbitrarily penetrating three-dimensional network structure, so compared with bulk solid materials, aerogels have relatively poor mechanical strength and are brittle. In practical applications, aerogels will inevitably be The ground is subject to irreparable mechanical damage, resulting in the destruction of its structural integrity and inherent properties.
  • the technical problem to be solved by the present invention is to overcome the inevitable irreparable mechanical damage of the aerogels in the prior art in practical applications, resulting in the destruction of their structural integrity and inherent properties, and a short service life. defects, thereby providing a self-healing aerogel.
  • the technical scheme adopted in the present invention is:
  • a self-healing aerogel is prepared according to the following steps:
  • the biomass polysaccharide solution with a mass fraction of ⁇ 5wt% and a polyvinyl alcohol aqueous solution with a mass fraction of 5wt%-20wt% are mixed according to a mass ratio of 100:(15-35) to prepare a composite hydrogel material, and then the composite hydrogel is formed. Freeze-drying the glue material to obtain a self-healing aerogel;
  • the average degree of polymerization of the polyvinyl alcohol is 1000-2000.
  • biomass polysaccharide is at least one of chitosan and sodium alginate.
  • the biomass polysaccharide solution is a chitosan solution
  • the chitosan solution is prepared from chitosan powder with a degree of deacetylation of 65%-90% and a dilute acid solution.
  • the dilute acid solution is an acetic acid solution.
  • the mass fraction of the acetic acid solution is 1-5%.
  • the raw materials for preparing the composite hydrogel material further include an aqueous solution of zwitterionic polyurethane with a mass fraction of 5wt%-20wt%.
  • the added mass ratio of the biomass polysaccharide solution, the zwitterionic polyurethane aqueous solution, and the polyvinyl alcohol aqueous solution is 100:(1-10):(15-35).
  • the zwitterionic polyurethane aqueous solution is prepared by mixing N,N-dihydroxyethyl isonicotine, hexamethylene diisocyanate and 1,3-propane sultone.
  • the preparation of the zwitterionic polyurethane aqueous solution includes the following steps:
  • the organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, and dimethyl sulfoxide, and/or, the catalyst is two Dibutyltin laurate catalyst.
  • the removing the organic solvent includes the step of drying the mixed solution of the zwitterionic polyurethane and the organic solvent at 80° C. for 24 hours.
  • preparation of the composite hydrogel material comprises the following steps:
  • freeze-drying of the composite hydrogel material to obtain the self-healing aerogel includes vacuum freeze-drying or supercritical drying of the composite hydrogel material.
  • the vacuum freeze-drying includes the following steps: placing the composite hydrogel material in a vacuum environment with a pressure of less than 5 Pa, and freeze-drying at -55° C. for 12-48 hours.
  • the supercritical drying includes the following steps: using ethanol as the supercritical drying medium, pre-filling the reactor with nitrogen of 2 MPa, then heating to 260° C. The pressure is slowly released at a speed of 2MPa/h until it is zero, and finally nitrogen is charged for 10-30min to remove the residual ethanol in the reactor. After the temperature is slowly lowered to room temperature, the aerogel is obtained and the pressure is less than 5Pa, and the time is 12- 48h.
  • the self-healing aerogel provided by the present invention is limited by the raw materials and preparation methods for preparing the self-healing aerogel, so that the molecular chain at the incision of the prepared aerogel can be cured under the action of water. A phenomenon of dissolution occurs, and then the anions and cations at both ends of the aerogel incision can move in the dissolved part, and the molecular chains can be reconnected through the electrostatic effect of ionic bonds. At the same time, hydrogen bonds also synergize with ionic bonds.
  • the incision is healed, so as to realize the self-healing of the aerogel, that is, the self-healing aerogel provided by the present invention can also exhibit a very low apparent density under the interaction of two chemical bonds, ionic bond and hydrogen bond. It has excellent mechanical properties, and has the ability of rapid self-healing at room temperature. It has good mechanical properties before and after self-healing, and the aerogel can be completely dissolved, has good biocompatibility, is environmentally friendly, and is good for human body. Non-toxic, can be widely used in medical care, textile and clothing, catalysis, aerospace, unmanned driving, thermal insulation foam, oil absorption or dust particle absorption and other fields.
  • the mechanical properties and self-healing properties of the self-healing aerogel can be controlled by adjusting the different ratios of the polyvinyl alcohol aqueous solution, the zwitterionic polyurethane aqueous solution and the chitosan solution. Healing properties to meet the needs of aerogels in different fields.
  • the self-healing aerogel provided by the present invention is prepared by selecting chitosan and polyvinyl alcohol as raw materials, wherein chitosan is derived from discarded shrimp shells and crab shells, and has the characteristics of low cost, while ethylene
  • the base polymer is a compound that can be used by bacteria as a carbon source and energy source, and has the characteristics of biodegradation and low price. By formulating two or more kinds of green and environmentally friendly materials into a solution and mixing, and then preparing a gas condensate.
  • the aerogel material has good green environmental protection performance.
  • the degree of deacetylation refers to the ratio of the number of deacetylated glucosamine units to the total number of glucosamine units, which is one of the most basic structural parameters of chitosan.
  • the higher the degree of deacetylation the more free amino groups on the molecular chain, and the better the solubility in acid.
  • the water absorption rate of chitosan is controlled by limiting the degree of deacetylation of chitosan. The water absorption rate increases with the increase of the deacetylation degree, and the increase of the water absorption rate is beneficial to the improvement of the self-healing effect.
  • the self-healing aerogel provided by the present invention by adding the zwitterionic polyurethane aqueous solution, because the zwitterionic polyurethane has super anti-biological pollution performance and excellent biocompatibility, and due to super electrostatic force, Zwitterionic polymers can form a hydrated layer on the surface of the material, thereby enhancing the self-healing properties of self-healing aerogels.
  • the self-healing aerogel provided by the present invention by limiting the preparation raw materials of the zwitterionic polyurethane aqueous solution, makes the prepared amphoteric polyurethane aqueous solution low in toxicity, so that the self-healing aerogel satisfies the characteristics of green environmental protection .
  • Fig. 1 is the microstructure diagram of the self-healing aerogel of Example 1 of the present invention.
  • Fig. 2 is the microstructure diagram of the self-healing aerogel of Example 2 of the present invention.
  • Fig. 3 is the microstructure diagram of the self-healing aerogel of Example 3 of the present invention.
  • Fig. 4 is the microstructure diagram of the self-healing aerogel of Example 4 of the present invention.
  • Fig. 5 (left) is the thermal insulation effect diagram of the self-healing aerogel of Example 1 of the present invention.
  • Fig. 5 (right) is the thermal insulation effect diagram of the self-healing aerogel of Example 2 of the present invention.
  • FIG. 6 is a graph showing the mechanical strength of the self-healing aerogels of Examples 1-4 of the present invention under 70% compressive strain
  • Example 7 is a schematic diagram of the microscopic self-healing process of the self-healing aerogel of Example 2 of the present invention.
  • Example 8 is a tensile stress-strain diagram of the self-healing aerogel of Example 2 of the present invention before and after self-healing.
  • the present invention refers to a kind of self-healing aerogel, and this self-healing aerogel is prepared according to the following steps:
  • the biomass polysaccharide solution with a mass fraction of ⁇ 5wt% and a polyvinyl alcohol aqueous solution with a mass fraction of 5wt%-20wt% are mixed according to a mass ratio of 100:(15-35) to prepare a composite hydrogel material, and then the composite hydrogel is formed. Freeze-drying the glue material to obtain a self-healing aerogel;
  • the average degree of polymerization of the polyvinyl alcohol is 1000-2000.
  • the polyvinyl alcohol aqueous solution is prepared according to the following steps: weigh a certain amount of polyvinyl alcohol, add deionized water according to the final mass fraction, and heat and stir in a water bath at 80°C for 1.5 hours to fully dissolve the polyvinyl alcohol particles , and then placed in a water bath at 60°C for 0.5h to remove air bubbles and keep warm.
  • the biomass polysaccharide is at least one of chitosan and sodium alginate
  • the biomass polysaccharide solution is a chitosan solution
  • the chitosan solution is prepared from chitosan powder with a degree of deacetylation of 65%-90% and a dilute acid solution.
  • the dilute acid solution is selected as an acetic acid solution.
  • acetic acid can make chitosan protonated, thereby promoting chitosan to dissolve in water, and acetic acid can form ionic bonds with chitosan, thereby enhancing the self-healing properties of aerogels.
  • the mass fraction of the acetic acid solution is 1-5%. If the concentration of acetic acid is too low, the chitosan solution will not dissolve completely, and if the concentration of acetic acid is too high, the solubility of chitosan in the chitosan solution will be reduced, and the precipitation of chitosan will prevent the preparation of aerogels.
  • the chitosan solution is prepared according to the following steps: adding chitosan powder to the dilute acid solution at room temperature, filtering off insoluble matter after stirring, and storing at room temperature for use.
  • an aqueous solution of zwitterionic polyurethane with a mass fraction of 5wt% to 20wt% can also be added when preparing the composite hydrogel material.
  • the mass ratio of the biomass polysaccharide solution, the zwitterionic polyurethane aqueous solution, and the polyvinyl alcohol aqueous solution is 100: (1-10): (15-35).
  • the zwitterionic polyurethane aqueous solution is set to be mixed with N,N-dihydroxyethylisonicotine, hexamethylene diisocyanate and 1,3-propane sultone prepared.
  • the preparation of the zwitterionic polyurethane aqueous solution specifically includes the following steps:
  • the organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, and dimethylsulfoxide;
  • the catalyst is preferably a dibutyltin dilaurate catalyst.
  • the removal of the organic solvent includes the step of drying the mixed solution of the zwitterionic polyurethane and the organic solvent at 80° C. for 24 hours. Specifically, removing the organic solvent includes pouring the mixed solution of the zwitterionic polyurethane and the organic solvent into a polytetrafluoroethylene tray, and drying in a blast drying oven at 80° C. for 24 hours.
  • the preparation of the composite hydrogel includes the following steps: after mixing the polyvinyl alcohol aqueous solution, the zwitterionic polyurethane aqueous solution and the chitosan solution evenly, ultrasonically mixing for 10-30 minutes to remove air bubbles to obtain a mixed solution; Freeze at 0°C for 10-20 hours; thaw the frozen mixed solution at room temperature for 1-5 hours; repeat the above freezing-thawing operation 1-5 times to obtain a composite hydrogel material.
  • the mixed solution after removing the bubbles can be poured into a specific mold, and then the mold and the mixed solution can be frozen-thawed together Just do it.
  • freeze drying is at least one of vacuum freeze drying and supercritical drying.
  • the vacuum freeze-drying includes the following steps: placing the composite hydrogel material in a vacuum environment with a pressure of less than 5 Pa, and freeze-drying at -55° C. for 12-48 hours.
  • the vacuum freeze drying step can be carried out in a vacuum freeze dryer.
  • the supercritical drying includes the following steps: using ethanol as the supercritical drying medium, pre-filling the reactor with nitrogen at 2MPa, then heating to 260°C at a heating rate of 50°C/h, holding for 2h, and then at a rate of 2MPa/h. Slowly release the pressure until zero, and finally fill with nitrogen for 10-30 minutes to remove the residual ethanol in the reactor. After the temperature is slowly lowered to room temperature, the aerogel is obtained and the pressure is pumped to less than 5Pa for 12-48h.
  • the reactor can optionally be inside a supercritical autoclave.
  • the aerogel prepared according to the above scheme has ionic bonds and hydrogen bonds, so that under the interaction of ionic bonds and hydrogen bonds, the aerogel has excellent self-healing properties and mechanical properties.
  • the present embodiment relates to a self-healing aerogel, which is prepared according to the following steps:
  • Preparation of polyvinyl alcohol aqueous solution Weigh 18.25g polyvinyl alcohol, add 131.25g deionized water, heat and stir in a water bath at 40°C for 0.5h, then raise the temperature of the water bath to 60°C, heat and stir for 0.5h, and then The temperature of the water bath was raised to 80 °C, heated and stirred for 1 h, and finally the temperature of the water bath was raised to 96 °C, heated and stirred for more than 6 h, so that the PVA particles were fully dissolved, and then placed in a water bath at 80 °C for 0.5 h. A polyvinyl alcohol aqueous solution with a mass fraction of 12.5% was obtained;
  • Preparation of composite hydrogel material take 4 g of the polyvinyl alcohol aqueous solution prepared in S1 and 16 g of the chitosan solution prepared in S2, mix the polyvinyl alcohol aqueous solution and the chitosan solution evenly, and ultrasonically for 15 minutes to remove the solution Then, pour the mixture into the mold, put the mold in the refrigerator, freeze at -30°C for 5 hours, take out the mold and place it at room temperature to thaw for 2 hours, and then repeat the freeze-thaw operation 3 to obtain a composite hydrogel.
  • Freeze drying put the composite hydrogel obtained in S3 into a freeze dryer whose cold trap temperature has been stabilized at -55°C for pre-cooling, and after 2 hours, place the pre-cooled aerogel in the iron of the freeze dryer. In the tray, start the vacuum pump to a pressure of less than 5Pa and freeze-dry for 24 hours to obtain a CPA-20 self-healing aerogel.
  • the aerogel obtained by the method can lift a weight 4000 times its own weight within 60s of self-healing, the mechanical strength under 70% compressive strain is 0.46MPa, the voids are relatively uniform, and the thermal conductivity is 0.046W/mk.
  • the microstructure of the aerogel is shown in Figure 1.
  • the present embodiment relates to a self-healing aerogel, which is prepared according to the following steps:
  • Preparation of polyvinyl alcohol aqueous solution Weigh 18.25g polyvinyl alcohol, add 131.25g deionized water, heat and stir in a water bath at 40°C for 0.5h, then raise the temperature of the water bath to 60°C, heat and stir for 0.5h, and then The temperature of the water bath was raised to 80 °C, heated and stirred for 1 h, and finally the temperature of the water bath was raised to 96 °C, heated and stirred for more than 6 h, so that the PVA particles were fully dissolved, and then placed in a water bath at 80 °C for 0.5 h. A polyvinyl alcohol aqueous solution with a mass fraction of 12.5% was obtained;
  • zwitterionic polyurethane aqueous solution N,N-dihydroxyethyl isonicotine (BINA), hexamethylene diisocyanate (HDI) and catalyst are reacted in an organic solvent at 80 ° C for 3-5 hours to synthesize Shape memory polyurethane, then add 1,3-propane sultone (1,3-PS) to carry out ring-opening reaction at 50 ° C for more than 6 hours to obtain a mixed solution of zwitterionic polyurethane and organic solvent, pour the solution into polytetrafluoroethylene In a vinyl fluoride tray, it was dried in a blast drying oven at 80°C for 24 hours, and the organic solvent was removed to obtain zwitterionic polyurethane.
  • the organic solvent is N,N-dimethylformamide
  • the catalyst is a dibutyltin dilaurate catalyst.
  • Preparation of composite hydrogel take 4 g of the polyvinyl alcohol aqueous solution prepared in S1, 16 g of the chitosan solution prepared in S2, and 1 g of the zwitterionic polyurethane aqueous solution prepared in S3, mix the polyvinyl alcohol aqueous solution, chitosan solution and After the zwitterionic polyurethane aqueous solution is evenly mixed, ultrasonicate for 15 minutes to remove the bubbles in the solution to obtain a mixed solution, then pour the mixed solution into the mold, put the mold into the refrigerator, freeze at -30 °C for 5 hours, and then take out the mold It was thawed at room temperature for 2 hours, and then the freeze-thaw operation was repeated 3 times to obtain a composite hydrogel.
  • Freeze drying put the composite hydrogel obtained in S4 into a freeze dryer whose cold trap temperature has been stabilized at -55°C for pre-cooling, and after 2 hours, place the pre-cooled aerogel in the iron of the freeze dryer. In the tray, start the vacuum pump until the pressure is less than 5Pa and freeze-dry for 24 hours to obtain ZCPA-20 self-healing aerogel.
  • the aerogel obtained by the method can lift a heavy object 6000 times its own weight within 60s of self-healing, the mechanical strength under 70% compressive strain is 0.6MPa, the voids are relatively uniform, and the thermal conductivity is 0.049W/mk.
  • the microstructure of the aerogel is shown in Figure 2.
  • the present embodiment relates to a self-healing aerogel, which is prepared according to the following steps:
  • Preparation of polyvinyl alcohol aqueous solution Weigh 18.25g polyvinyl alcohol, add 131.25g deionized water, heat and stir in a water bath at 40°C for 0.5h, then raise the temperature of the water bath to 60°C, heat and stir for 0.5h, and then The temperature of the water bath was raised to 80 °C, heated and stirred for 1 h, and finally the temperature of the water bath was raised to 96 °C, heated and stirred for more than 6 h, so that the PVA particles were fully dissolved, and then placed in a water bath at 80 °C for 0.5 h. A polyvinyl alcohol aqueous solution with a mass fraction of 12.5% was obtained;
  • zwitterionic polyurethane aqueous solution N,N-dihydroxyethyl isonicotine (BINA), hexamethylene diisocyanate (HDI) and catalyst are reacted in an organic solvent at 80 ° C for 3-5 hours to synthesize Shape memory polyurethane, then add 1,3-propane sultone (1,3-PS) to carry out ring-opening reaction at 50 ° C for more than 6 hours to obtain a mixed solution of zwitterionic polyurethane and organic solvent, pour the solution into polytetrafluoroethylene In a vinyl fluoride tray, it was dried in a blast drying oven at 80°C for 24 hours, and the organic solvent was removed to obtain zwitterionic polyurethane.
  • the organic solvent is N,N-dimethylformamide
  • the catalyst is a dibutyltin dilaurate catalyst.
  • Preparation of composite hydrogel take 5 g of the polyvinyl alcohol aqueous solution prepared in S1, 15 g of the chitosan solution prepared in S2, and 1 g of the zwitterionic polyurethane aqueous solution prepared in S3, mix the polyvinyl alcohol aqueous solution, chitosan solution and After the zwitterionic polyurethane aqueous solution is evenly mixed, ultrasonicate for 15 minutes to remove the bubbles in the solution to obtain a mixed solution, then pour the mixed solution into the mold, put the mold into the refrigerator, freeze at -30 °C for 5 hours, and then take out the mold It was thawed at room temperature for 2 hours, and then the freeze-thaw operation was repeated 3 times to obtain a composite hydrogel.
  • Freeze drying put the composite hydrogel obtained in S4 into a freeze dryer whose cold trap temperature has been stabilized at -55°C for pre-cooling, and after 2 hours, place the pre-cooled aerogel in the iron of the freeze dryer. In the tray, start the vacuum pump to a pressure of less than 5Pa and freeze-dry for 24 hours to obtain ZCPA-25 self-healing aerogel.
  • the aerogel obtained by the method can lift a weight 5000 times its own weight within 60s of self-healing, the mechanical strength under 70% compressive strain is 0.75MPa, the voids are relatively uniform, and the thermal conductivity is 0.053W/mk.
  • the microstructure of the aerogel is shown in Figure 3.
  • the present embodiment relates to a self-healing aerogel, which is prepared according to the following steps:
  • Preparation of polyvinyl alcohol aqueous solution Weigh 18.25g polyvinyl alcohol, add 131.25g deionized water, heat and stir in a water bath at 40°C for 0.5h, then raise the temperature of the water bath to 60°C, heat and stir for 0.5h, and then The temperature of the water bath was raised to 80 °C, heated and stirred for 1 h, and finally the temperature of the water bath was raised to 96 °C, heated and stirred for more than 6 h, so that the PVA particles were fully dissolved, and then placed in a water bath at 80 °C for 0.5 h. A polyvinyl alcohol aqueous solution with a mass fraction of 12.5% was obtained;
  • zwitterionic polyurethane aqueous solution N,N-dihydroxyethyl isonicotine (BINA), hexamethylene diisocyanate (HDI) and catalyst are reacted in an organic solvent at 80 ° C for 3-5 hours to synthesize Shape memory polyurethane, then add 1,3-propane sultone (1,3-PS) to carry out ring-opening reaction at 50 ° C for more than 6 hours to obtain a mixed solution of zwitterionic polyurethane and organic solvent, pour the solution into polytetrafluoroethylene In a vinyl fluoride tray, it was dried in a blast drying oven at 80°C for 24 hours, and the organic solvent was removed to obtain zwitterionic polyurethane.
  • the organic solvent is N,N-dimethylformamide
  • the catalyst is a dibutyltin dilaurate catalyst.
  • Preparation of composite hydrogel take 6 g of the polyvinyl alcohol aqueous solution prepared in S1, 14 g of the chitosan solution prepared in S2, and 1 g of the zwitterionic polyurethane aqueous solution prepared in S3, mix the polyvinyl alcohol aqueous solution, chitosan solution and After the zwitterionic polyurethane aqueous solution is evenly mixed, ultrasonicate for 15 minutes to remove the bubbles in the solution to obtain a mixed solution, then pour the mixed solution into the mold, put the mold into the refrigerator, freeze at -30 °C for 5 hours, and then take out the mold It was thawed at room temperature for 2 hours, and then the freeze-thaw operation was repeated 3 times to obtain a composite hydrogel.
  • Freeze drying put the composite hydrogel obtained in S4 into a freeze dryer whose cold trap temperature has been stabilized at -55°C for pre-cooling, and after 2 hours, place the pre-cooled aerogel in the iron of the freeze dryer. In the tray, start the vacuum pump to a pressure of less than 5Pa and freeze-dry for 24 hours to obtain ZCPA-30 self-healing aerogel.
  • the aerogel obtained by the method can lift a weight 5000 times its own weight within 60s of self-healing, the mechanical strength under 70% compressive strain is 1.3MPa, the voids are relatively uniform, and the thermal conductivity is 0.068W/mk.
  • the microstructure of the aerogel is shown in Figure 4.
  • the thermal insulation effect of the self-healing aerogel provided in Examples 1-2 was tested by using the IKA RCT Basic stirring hot stage. First, the hot stage was heated to 120°C, and then the The self-healing aerogel was placed on the hot stage, and after heating for 5 minutes, the self-healing aerogel was photographed by the FLUKE Ti110 infrared thermal imager. The test results are shown in Figure 5, and the left side of Figure 5 is the implementation The thermal insulation effect diagram of the self-healing aerogel provided in Example 1, the right side of FIG. 5 is the thermal insulation effect diagram of the self-healing aerogel provided in Example 2. The thermal insulation effect of the self-healing aerogel is better than that of Example 2.
  • the mechanical properties of the self-healing aerogels provided in Examples 1-4 were tested according to GB/T 1041-1992 compression test gel. The test results are shown in Figure 6.
  • the mechanical strength is 0.46MPa; the mechanical strength of Example 2 under 70% compressive strain is 0.6MPa, the mechanical strength of Example 3 under 70% compressive strain is 0.75MPa; the mechanical strength of Example 4 under 70% compressive strain is 1.3MPa.
  • Example 2 The self-healing effect of the self-healing aerogel provided in Example 2 was tested by using a thermal field emission scanning electron microscope of the NGB4-DXS-10AC model of Hitachi, Japan.
  • the thermal insulation properties of the self-healing aerogels provided in Examples 1-4 were tested according to the GB 3399-82 test method for thermal conductivity of plastics.
  • the test results showed that the thermal conductivity of Example 1 was 0.046W/mk;
  • the thermal conductivity of 2 is 0.049W/mk;
  • the thermal conductivity of Example 3 is 0.053W/mk;
  • the thermal conductivity of Example 4 is 0.068W/mk.

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Abstract

一种可自愈合气凝胶，可自愈合气凝胶按照以下步骤制备而成：将质量分数≤5wt％的生物质多糖溶液与质量分数为5wt％-20wt％的聚乙烯醇水溶液按照100：(15-35)的质量比混合制备形成复合水凝胶材料，然后将复合水凝胶材料进行冷冻干燥即得可自愈合气凝胶；其中，聚乙烯醇的平均聚合度为1000-2000。该自愈合气凝胶在离子键和氢键两种化学键的相互作用下，在非常低的表观密度下也能显示出出色的机械性能，且在室温下具有快速自愈的能力，自修复前后均具有良好的力学性能，且该气凝胶可完全溶解，具有良好的生物相容性，对环境友好，对人体无毒。

Description

一种可自愈合气凝胶 技术领域
本发明涉及气凝胶领域，具体涉及一种可自愈合气凝胶。
背景技术
气凝胶，又称干凝胶，是一种固体物质形态，是密度最小的固体，约为3千克每立方米。一般常见的气凝胶为硅气凝胶，气凝胶的种类很多，有硅系，碳系，硫系，金属氧化物系，金属系等等，任何物质的凝胶只要可以经干燥除去内部溶剂后，又可基本保持其形状不变，且产物高孔隙率、低密度，则皆可以称之为气凝胶。
气凝胶作为一种结构可控的纳米多孔材料，具有比表面积高、可调孔径、可调骨架和特殊的表面性能等独特的优点，近年来，其在吸附、催化、传感器、热绝缘体、电极、生物技术等诸多高科技领域的应用也越来越受到重视。
但是，正是由于气凝胶具有任意贯通的三维网络结构，因此，与块状固体材料相比，气凝胶的机械强度相对较差且易碎，在实际应用中，气凝胶会不可避免地受到不可弥补的力学损伤，从而导致其结构完整性和固有性能被破坏。
现在，人们越来越多的认识到，延长气凝胶使用寿命的关键在于使其获得自愈合能力。因此，开发具有自修复功能的气凝胶，使其在损伤后能够回复结构完整性和固有性能是非常必要的。
发明内容
因此，本发明要解决的技术问题在于克服现有技术中的气凝胶在实际应用中会不可避免地受到不可弥补的力学损伤，从而导致其结构完整性和固有性能被破坏，使用寿命较短的缺陷，从而提供一种可自愈合的气凝胶。
为解决上述技术问题，本发明采用的技术方案为：
一种可自愈合气凝胶，按照以下步骤制备而成：
将质量分数≤5wt％的生物质多糖溶液与质量分数为5wt％-20wt％的聚乙烯醇水溶液按照100：(15-35)的质量比混合制备形成复合水凝胶材料，然后将复合水凝胶材料进行冷冻干燥即得可自愈合气凝胶；
其中，所述聚乙烯醇的平均聚合度为1000-2000。
进一步的，所述生物质多糖为壳聚糖、海藻酸钠中的至少一种。
进一步的，所述生物质多糖溶液为壳聚糖溶液，所述壳聚糖溶液由脱乙酰度为65％-90％的壳聚糖粉末与稀酸溶液配制而成。
进一步的，所述稀酸溶液为乙酸溶液。
进一步的，所述乙酸溶液的质量分数为1-5％。
进一步的，制备所述复合水凝胶材料的原材料还包括质量分数为5wt％-20wt％的两性离子聚氨酯水溶液。
进一步的，所述生物质多糖溶液、两性离子聚氨酯水溶液、聚乙烯醇水溶液的添加质量比为100：(1-10)：(15-35)。
进一步的，所述两性离子聚氨酯水溶液由N,N-二羟乙基异烟碱、六亚甲基二异氰酸酯以及1,3-丙磺酸内酯混合制备而成。
进一步的，所述两性离子聚氨酯水溶液制备包括以下步骤：
将N,N-二羟乙基异烟碱，六亚甲基二异氰酸酯以及催化剂在有机溶剂中80℃下反应3-5小时，合成形状记忆聚氨酯，再加入1,3-丙磺酸内酯，在50℃下进行开环反应6小时以上，得到两性离子聚氨酯与有机溶剂的混合溶液，去 除有机溶剂，得到两性离子聚氨酯，将两性离子聚氨酯溶于水即得两性离子聚氨酯水溶液。
进一步的，所述有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二甲基亚砜中的至少一种，和/或，所述催化剂为二月桂酸二丁基锡催化剂。
进一步的，所述去除有机溶剂包括将所述两性离子聚氨酯与有机溶剂的混合溶液在80℃下干燥24h的步骤。
进一步的，所述制备复合水凝胶材料包括以下步骤：
将复合水凝胶材料的原料混合均匀后，超声混合10-30分钟去除气泡，得到混合液；
将所述混合液在-50℃-0℃下冷冻10-20h；
将完成冷冻的混合液在室温下解冻1-5h；
重复上述冷冻-解冻操作1-5次，得到复合水凝胶材料。
进一步的，所述将复合水凝胶材料进行冷冻干燥即得可自愈合气凝胶包括将所述复合水凝胶材料进行真空冷冻干燥或超临界干燥。
进一步的，所述真空冷冻干燥包括以下步骤：将复合水凝胶材料置于压强小于5Pa的真空环境中，于-55℃下冷冻干燥12-48h。
进一步的，所述超临界干燥包括以下步骤：以乙醇作为超临界干燥介质，往反应器内预充2MPa的氮气，再以50℃/h的升温速度加热到260℃，保温2h后，再以2MPa/h的速度缓慢释放压力直至为零，最后再充入氮气10～30min以除去反应器内残留的乙醇，待温度缓慢降至室温，得到气凝胶抽至压强小于5Pa，时间为12-48h。
本发明技术方案，具有如下优点：
1.本发明提供的可自愈合气凝胶，通过对制备自愈合气凝胶的原材料及制备方法进行限定，使得制备得到的气凝胶的切口处的分子链在水的作用下会出现一种溶解的现象，然后气凝胶切口两端的阴阳离子可以在溶解的部分运动，通过离子键的静电作用可以将分子链重新连接，与此同时，氢键也和离子键产生协同作用，使切口愈合，从而实现气凝胶的自愈合，即本发明提供的自愈合气凝胶在离子键和氢键两种化学键的相互作用下，在非常低的表观密度下也能显示出出色的机械性能，且在室温下具有快速自愈的能力，自修复前后均具有良好的力学性能，且该气凝胶可完全溶解，具有良好的生物相容性，对环境友好，对人体无毒，可广泛应用于医疗保健、纺织服装、催化、航空航天、无人驾驶、隔热泡沫、油污吸收或者粉尘颗粒吸收等领域。
2.本发明提供的可自愈合气凝胶，通过调节聚乙烯醇水溶液，两性离子聚氨酯水溶液以及壳聚糖溶液的不同配比可以控制生成的可自愈合气凝胶的力学性能和自愈合性能以满足不同领域气凝胶的需求。
3.本发明提供的可自愈合气凝胶，通过选用壳聚糖以及聚乙烯醇作为制备原料，其中，壳聚糖来源于废弃的虾壳和蟹壳，具有成本低廉的特点，而乙烯基聚合物是可被细菌作为碳源和能源利用的化合物，具有可生物降解、价格低廉等特点，通过将两种及两种以上的绿色环保的材料配制成溶液并进行混合，然后制备出气凝胶材料，使得气凝胶材料具有良好的绿色环保性能。
4.本发明提供的可自愈合气凝胶，脱乙酰度是指脱去乙酰基的葡萄糖胺单元数占总的葡萄糖胺单元数的比例，其是考察壳聚糖最基本的结构参数之一，脱乙酰度越高，分子链上的游离氨基越多，在酸中的溶解性越好，本申请通过限定壳聚糖的脱乙酰度来控制壳聚糖的吸水率，壳聚糖的吸水率随着脱乙酰度的增大而增大，吸水率的增加有利于自修复效果的提高。
5.本发明提供的可自愈合气凝胶，通过加入两性离子聚氨酯水溶液，由于两性离子聚氨酯具有超强的抗生物污染性能以及优异的生物相容性，且由于超强的静电作用力，两性离子聚合物能在材料表面形成水合层，从而增强自愈合气凝胶的自愈合性能。
6.本发明提供的可自愈合气凝胶，通过限定两性离子聚氨酯水溶液的制备原料，使得制备得到的两性聚氨酯水溶液的毒性较低，从而使得可自愈合气凝胶满足绿色环保的特性。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例1的可自愈合气凝胶的微观结构图；
图2是本发明实施例2的可自愈合气凝胶的微观结构图；
图3是本发明实施例3的可自愈合气凝胶的微观结构图；
图4是本发明实施例4的可自愈合气凝胶的微观结构图；
图5(左)是本发明实施例1的可自愈合气凝胶的隔热效果图；
图5(右)是本发明实施例2的可自愈合气凝胶的隔热效果图；
图6是本发明实施例1-4的可自愈合气凝胶在70％压缩应变下的力学强度曲线图；
图7是本发明实施例2的可自愈合气凝胶的微观自愈合过程示意图；
图8是本发明实施例2的可自愈合气凝胶的自愈合前后的拉伸应力-应变图。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
本发明是指一种可自愈合气凝胶，该可自愈合气凝胶按照以下步骤制备得到:
将质量分数≤5wt％的生物质多糖溶液与质量分数为5wt％-20wt％的聚乙烯醇水溶液按照100：(15-35)的质量比混合制备形成复合水凝胶材料，然后将复合水凝胶材料进行冷冻干燥即得可自愈合气凝胶；
其中，所述聚乙烯醇的平均聚合度为1000-2000。
具体的，聚乙烯醇水溶液按照如下步骤配制：称取一定量的聚乙烯醇，按照最终的质量分数加入去离子水，在80℃的水浴锅中加热搅拌1.5h，让聚乙烯醇颗粒充分溶解，再在60℃的水浴锅中静置0.5h，除去气泡并保温。
可选的，生物质多糖为壳聚糖、海藻酸钠中的至少一种
当生物质多糖溶液为壳聚糖溶液时，壳聚糖溶液由脱乙酰度为65％-90％的壳聚糖粉末与稀酸溶液配制而成。
作为优选，稀酸溶液选择为乙酸溶液。乙酸的加入可以使得壳聚糖质子化，从而促进壳聚糖融溶于水，同时乙酸可以与壳聚糖形成离子键，从而加强气凝胶的自愈合性能。
具体的，乙酸溶液的质量分数为1-5％。乙酸浓度太低会使壳聚糖溶液溶解不完全，乙酸浓度太高会使壳聚糖溶液中的壳聚糖溶解度变小，使壳聚糖析出导致无法制备出气凝胶。
具体的，壳聚糖溶液按照如下步骤配制：将壳聚糖粉末在常温下加入到稀酸溶液中，搅拌后滤去不溶物，室温存放待用。
优选的，为增强可自愈合气凝胶的自愈合能力，在制备复合水凝胶材料时还可以加入质量分数为5wt％-20wt％的两性离子聚氨酯水溶液。
具体的，生物质多糖溶液、两性离子聚氨酯水溶液、聚乙烯醇水溶液的添加质量比为100：(1-10)：(15-35)。
优选的，为减小两性离子聚氨酯水溶液的毒性，将两性离子聚氨酯水溶液设置为由N,N-二羟乙基异烟碱、六亚甲基二异氰酸酯以及1,3-丙磺酸内酯混合制备而成。
两性离子聚氨酯水溶液制备具体包括以下步骤：
将N,N-二羟乙基异烟碱，六亚甲基二异氰酸酯以及催化剂在有机溶剂中80℃下反应3-5小时，合成形状记忆聚氨酯，再加入1,3-丙磺酸内酯，在50℃下进行开环反应6小时以上，得到两性离子聚氨酯与有机溶剂的混合溶液，去除有机溶剂，得到两性离子聚氨酯，将两性离子聚氨酯溶于水即得两性离子聚氨酯水溶液。
其中，有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二甲基亚砜中的至少一种；所述催化剂优选为二月桂酸二丁基锡催化剂。
去除有机溶剂包括将所述两性离子聚氨酯与有机溶剂的混合溶液在80℃下干燥24h的步骤。具体的，去除有机溶剂包括将所述两性离子聚氨酯与有机溶剂的混合溶液倒入聚四氟乙烯盘中，在80℃的鼓风干燥箱中干燥24h。
复合水凝胶的制备包括以下步骤：将聚乙烯醇水溶液，两性离子聚氨酯水溶液以及壳聚糖溶液混合均匀后，超声混合10-30分钟去除气泡，得到混合液；将混合液在-50℃-0℃下冷冻10-20h；将完成冷冻的混合液在室温下解冻1-5h；重复上述冷冻-解冻操作1-5次，得到复合水凝胶材料。
其中，如需要将气凝胶制备成特定的形状，即可在制备复合水凝胶时，将除去气泡后的混合液倒入至特定的模具中，再将模具与混合液一起进行冷冻-解冻操作即可。
作为可选的实施例，冷冻干燥为真空冷冻干燥和超临界干燥中的至少一种。
其中，真空冷冻干燥包括以下步骤：将复合水凝胶材料置于压强小于5Pa的真空环境中，于-55℃下冷冻干燥12-48h。
真空冷冻干燥步骤可在真空冷冻干燥机中进行。
超临界干燥包括以下步骤：以乙醇作为超临界干燥介质，往反应器内预充2MPa的氮气，再以50℃/h的升温速度加热到260℃，保温2h后，再以2MPa/h的速度缓慢释放压力直至为零，最后再充入氮气10～30min以除去反应器内残留的乙醇，待温度缓慢降至室温，得到气凝胶抽至压强小于5Pa，时间为12-48h。
反应器可选为超临界高压釜内。
按照上述方案制备出的气凝胶，具有离子键以及氢键，从而使得在离子键与氢键的相互作用下，气凝胶具有优异的自愈合性能以及力学性能。
实施例1
本实施例涉及一种可自愈合气凝胶，按照以下步骤制备得到：
S1、聚乙烯醇水溶液配制：称取18.25g聚乙烯醇，加入131.25g去离子水，在40℃的水浴锅中加热搅拌0.5h，再将水浴锅温度升至60℃加热搅拌0.5h，然后将水浴锅温度升至80℃加热搅拌1h，最后水浴锅温度升至96℃加热搅拌6h以上，让PVA颗粒充分溶解，再在80℃的水浴锅中静置0.5h，除去气泡并保温，配制得到质量分数为12.5％的聚乙烯醇水溶液；
S2、壳聚糖溶液配制：称取脱乙酰度为85％的壳聚糖粉末4g，量取质量分数为1％的乙酸96g，在常温下降壳聚糖粉末加入至乙酸水溶液中，搅拌后，滤去不溶物，配制得到质量分数为2％的壳聚糖溶液，室温存放待用；
S3、复合水凝胶材料制备：取S1配制得到的聚乙烯醇水溶液4g，S2配制得到的壳聚糖溶液16g，将聚乙烯醇水溶液与壳聚糖溶液混合均匀后，超声15分钟，除去溶液中的气泡，得到混合液，然后将混合液倒入至模具中，将模具放进冰箱中，于-30℃下冷冻5h后，取出模具放置在室温下解冻2h，然后重复冷冻-解冻操作3次，得到复合水凝胶。
S4、冷冻干燥：将S3得到的复合水凝胶放入冷阱温度已经稳定在-55℃的冷冻干燥机中预冷，2小时后把预冷到的气凝胶放置于冷冻干燥机的铁盘中，启动真空泵抽至压强小于5Pa冷冻干燥24小时后，得到CPA-20可自愈合气凝胶。
本方法得到的气凝胶自愈合60s内能拉起自身重量4000倍的重物，70％压缩应变下的力学强度为0.46MPa，空隙较为均匀，导热系数为0.046W/mk。气凝胶的微观结构图见图1。
实施例2
本实施例涉及一种可自愈合气凝胶，按照以下步骤制备得到：
S1、聚乙烯醇水溶液配制：称取18.25g聚乙烯醇，加入131.25g去离子水，在40℃的水浴锅中加热搅拌0.5h，再将水浴锅温度升至60℃加热搅拌0.5h，然后将水浴锅温度升至80℃加热搅拌1h，最后水浴锅温度升至96℃加热搅拌6h以上，让PVA颗粒充分溶解，再在80℃的水浴锅中静置0.5h，除去气泡并保温，配制得到质量分数为12.5％的聚乙烯醇水溶液；
S2、壳聚糖溶液配制：称取脱乙酰度为85％的壳聚糖粉末4g，量取质量分数为1％的乙酸96g，在常温下降壳聚糖粉末加入至乙酸水溶液中，搅拌后，滤去不溶物，配制得到质量分数为2％的壳聚糖溶液，室温存放待用；
S3、两性离子聚氨酯水溶液配制：将N,N-二羟乙基异烟碱(BINA)，六亚甲基二异氰酸酯(HDI)以及催化剂在有机溶剂中在80℃下反应3-5小时，合成形状记忆聚氨酯，再加入1,3-丙磺酸内酯(1,3-PS)在50℃下进行开环反应6小时以上得到两性离子聚氨酯与有机溶剂的混合溶液，把溶液倒入聚四氟乙烯盘中，在80℃的鼓风干燥箱中干燥24h，除掉有机溶剂，得到两性离子聚氨酯，最后取部分两性离子聚氨酯溶于水，配制得到质量分数为10wt％的两性离子聚氨酯水溶液。其中所述有机溶剂为N,N-二甲基甲酰胺，所述催化剂为二月桂酸二丁基锡催化剂。
S4、复合水凝胶制备：取S1配制得到的聚乙烯醇水溶液4g，S2配制得到的壳聚糖溶液16g，S3配制得到的两性离子聚氨酯水溶液1g，将聚乙烯醇水溶液，壳聚糖溶液以及两性离子聚氨酯水溶液混合均匀后，超声15分钟，除去溶液中的气泡，得到混合液，然后将混合液倒入至模具中，将模具放进冰箱中，于-30℃下冷冻5h后，取出模具放置在室温下解冻2h，然后重复冷冻-解冻操作3次，得到复合水凝胶。
S5、冷冻干燥：将S4得到的复合水凝胶放入冷阱温度已经稳定在-55℃的冷冻干燥机中预冷，2小时后把预冷到的气凝胶放置于冷冻干燥机的铁盘中， 启动真空泵抽至压强小于5Pa冷冻干燥24小时后，得到ZCPA-20可自愈合气凝胶。
本方法得到的气凝胶自愈合60s内能拉起自身重量6000倍的重物，70％压缩应变下的力学强度为0.6MPa，空隙较为均匀，导热系数为0.049W/mk。气凝胶的微观结构图见图2。
实施例3
本实施例涉及一种可自愈合气凝胶，按照以下步骤制备得到：
S1、聚乙烯醇水溶液配制：称取18.25g聚乙烯醇，加入131.25g去离子水，在40℃的水浴锅中加热搅拌0.5h，再将水浴锅温度升至60℃加热搅拌0.5h，然后将水浴锅温度升至80℃加热搅拌1h，最后水浴锅温度升至96℃加热搅拌6h以上，让PVA颗粒充分溶解，再在80℃的水浴锅中静置0.5h，除去气泡并保温，配制得到质量分数为12.5％的聚乙烯醇水溶液；
S2、壳聚糖溶液配制：称取脱乙酰度为85％的壳聚糖粉末4g，量取质量分数为1％的乙酸96g，在常温下降壳聚糖粉末加入至乙酸水溶液中，搅拌后，滤去不溶物，配制得到质量分数为2％的壳聚糖溶液，室温存放待用；
S3、两性离子聚氨酯水溶液配制：将N,N-二羟乙基异烟碱(BINA)，六亚甲基二异氰酸酯(HDI)以及催化剂在有机溶剂中在80℃下反应3-5小时，合成形状记忆聚氨酯，再加入1,3-丙磺酸内酯(1,3-PS)在50℃下进行开环反应6小时以上得到两性离子聚氨酯与有机溶剂的混合溶液，把溶液倒入聚四氟乙烯盘中，在80℃的鼓风干燥箱中干燥24h，除掉有机溶剂，得到两性离子聚氨酯，最后取部分两性离子聚氨酯溶于水，配制得到质量分数为10wt％的两性离子聚氨酯水溶液。其中所述有机溶剂为N,N-二甲基甲酰胺，所述催化剂为二月桂酸二丁基锡催化剂。
S4、复合水凝胶制备：取S1配制得到的聚乙烯醇水溶液5g，S2配制得到的壳聚糖溶液15g，S3配制得到的两性离子聚氨酯水溶液1g，将聚乙烯醇水溶液，壳聚糖溶液以及两性离子聚氨酯水溶液混合均匀后，超声15分钟，除去溶液中的气泡，得到混合液，然后将混合液倒入至模具中，将模具放进冰箱中，于-30℃下冷冻5h后，取出模具放置在室温下解冻2h，然后重复冷冻-解冻操作3次，得到复合水凝胶。
S5、冷冻干燥：将S4得到的复合水凝胶放入冷阱温度已经稳定在-55℃的冷冻干燥机中预冷，2小时后把预冷到的气凝胶放置于冷冻干燥机的铁盘中，启动真空泵抽至压强小于5Pa冷冻干燥24小时后，得到ZCPA-25可自愈合气凝胶。
本方法得到的气凝胶自愈合60s内能拉起自身重量5000倍的重物，70％压缩应变下的力学强度为0.75MPa，空隙较为均匀，导热系数为0.053W/mk。气凝胶的微观结构图见图3。
实施例4
本实施例涉及一种可自愈合气凝胶，按照以下步骤制备得到：
S1、聚乙烯醇水溶液配制：称取18.25g聚乙烯醇，加入131.25g去离子水，在40℃的水浴锅中加热搅拌0.5h，再将水浴锅温度升至60℃加热搅拌0.5h，然后将水浴锅温度升至80℃加热搅拌1h，最后水浴锅温度升至96℃加热搅拌6h以上，让PVA颗粒充分溶解，再在80℃的水浴锅中静置0.5h，除去气泡并保温，配制得到质量分数为12.5％的聚乙烯醇水溶液；
S2、壳聚糖溶液配制：称取脱乙酰度为85％的壳聚糖粉末4g，量取质量分数为1％的乙酸96g，在常温下降壳聚糖粉末加入至乙酸水溶液中，搅拌后，滤去不溶物，配制得到质量分数为2％的壳聚糖溶液，室温存放待用；
S3、两性离子聚氨酯水溶液配制：将N,N-二羟乙基异烟碱(BINA)，六亚甲基二异氰酸酯(HDI)以及催化剂在有机溶剂中在80℃下反应3-5小时，合成形状记忆聚氨酯，再加入1,3-丙磺酸内酯(1,3-PS)在50℃下进行开环反应6小时以上得到两性离子聚氨酯与有机溶剂的混合溶液，把溶液倒入聚四氟乙烯盘中，在80℃的鼓风干燥箱中干燥24h，除掉有机溶剂，得到两性离子聚氨酯，最后取部分两性离子聚氨酯溶于水，配制得到质量分数为10wt％的两性离子聚氨酯水溶液。其中所述有机溶剂为N,N-二甲基甲酰胺，所述催化剂为二月桂酸二丁基锡催化剂。
S4、复合水凝胶制备：取S1配制得到的聚乙烯醇水溶液6g，S2配制得到的壳聚糖溶液14g，S3配制得到的两性离子聚氨酯水溶液1g，将聚乙烯醇水溶液，壳聚糖溶液以及两性离子聚氨酯水溶液混合均匀后，超声15分钟，除去溶液中的气泡，得到混合液，然后将混合液倒入至模具中，将模具放进冰箱中，于-30℃下冷冻5h后，取出模具放置在室温下解冻2h，然后重复冷冻-解冻操作3次，得到复合水凝胶。
S5、冷冻干燥：将S4得到的复合水凝胶放入冷阱温度已经稳定在-55℃的冷冻干燥机中预冷，2小时后把预冷到的气凝胶放置于冷冻干燥机的铁盘中，启动真空泵抽至压强小于5Pa冷冻干燥24小时后，得到ZCPA-30可自愈合气凝胶。
本方法得到的气凝胶自愈合60s内能拉起自身重量5000倍的重物，70％压缩应变下的力学强度为1.3MPa，空隙较为均匀，导热系数为0.068W/mk。气凝胶的微观结构图见图4。
试验例1：
采用IKA RCT Basic搅拌热台对实施例1-2提供的可自愈合气凝胶的隔热效果进行检测，首先将热台加热至120℃，然后将实施例1以及实施例2提供 的可自愈合气凝胶放置在热台上，加热5min后，利用FLUKE Ti110红外热成像仪对可自愈合气凝胶进行拍摄，检测结果如图5所示，其中，图5左侧为实施例1提供的可自愈合气凝胶的隔热效果图，图5右侧为实施例2提供的可自愈合气凝胶的隔热效果图，根据检测显示，实施例1提供的可自愈合气凝胶隔热效果要优于实施例2。
试验例2：
根据GB/T 1041-1992压缩实验凝胶对实施例1-4提供的可自愈合气凝胶的力学性能进行检测，检测结果如图6所示，实施例1在70％压缩应变下的力学强度为0.46MPa；实施例2在70％压缩应变下的力学强度为0.6MPa，实施例3在70％压缩应变下的力学强度为0.75MPa；实施例4在70％压缩应变下的力学强度为1.3MPa。
试验例3：
采用日本日立公司NGB4-DXS-10AC型号的热场发射扫描电镜对实施例2提供的自愈合气凝胶的自愈合效果进行检测。
首先在实施例2提供的可自愈合气凝胶上形成缺口(图中黑色框线所示部分)，然后在切口处均匀地喷少量的水，观察可自愈合气凝胶的愈合情况，检测结果如图7所示，从微观结构可以看出，实施例2提供的自愈合气凝胶愈合效果明显。
试验例4：
根据GB 13022-1991塑料-薄膜拉伸性能试验对实施例2提供的可自愈合气凝胶自愈前后的力学性能进行检测，检测结果图8所示，初始样品在应变为210％时断裂，此时的应力为0.27MPa；自愈合后的样品在应变为340％时断裂，此时的应力为0.36MPa。
试验例5：
根据GB 3399-82塑料导热系数试验方法对实施例1-4提供的可自愈合气凝胶的隔热性能进行检测，检测结果显示，实施例1的导热系数为0.046W/mk；实施例2的导热系数为0.049W/mk；实施例3的导热系数为0.053W/mk；实施例4的导热系数为0.068W/mk。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种可自愈合气凝胶，其特征在于，按照以下步骤制备而成：
    将质量分数≤5wt％的生物质多糖溶液与质量分数为5wt％-20wt％的聚乙烯醇水溶液按照100：(15-35)的质量比混合制备形成复合水凝胶材料，然后将复合水凝胶材料进行冷冻干燥即得可自愈合气凝胶；
    其中，所述聚乙烯醇的平均聚合度为1000-2000。
  2. 根据权利要求1所述的可自愈合气凝胶，其特征在于，所述生物质多糖为壳聚糖、海藻酸钠中的至少一种。
  3. 根据权利要求2所述的可自愈合气凝胶，其特征在于，所述生物质多糖溶液为壳聚糖溶液，所述壳聚糖溶液由脱乙酰度为65％-90％的壳聚糖粉末与质量分数为1-5％的乙酸溶液配制而成。
  4. 根据权利要求1-3中任一项所述的可自愈合气凝胶，其特征在于，制备所述复合水凝胶材料的原材料还包括质量分数为5wt％-20wt％的两性离子聚氨酯水溶液。
  5. 根据权利要求1-4中任一项所述的可自愈合气凝胶，其特征在于，所述生物质多糖溶液、两性离子聚氨酯水溶液、聚乙烯醇水溶液的添加质量比为100：(1-10)：(15-35)。
  6. 根据权利要求4或5所述的可自愈合气凝胶，其特征在于，所述两性离子聚氨酯水溶液由N,N-二羟乙基异烟碱、六亚甲基二异氰酸酯以及1,3-丙磺酸内酯混合制备而成。
  7. 根据权利要求6所述的可自愈合气凝胶，其特征在于，所述两性离子聚氨酯水溶液制备包括以下步骤：
    将N,N-二羟乙基异烟碱，六亚甲基二异氰酸酯以及催化剂在有机溶剂中80℃下反应3-5小时，合成形状记忆聚氨酯，再加入1,3-丙磺酸内酯，在50℃下进行开环反应6小时以上，得到两性离子聚氨酯与有机溶剂的混合溶液，去除有机溶剂，得到两性离子聚氨酯，将两性离子聚氨酯溶于水即得两性离子聚氨酯水溶液。
  8. 根据权利要求7所述的可自愈合气凝胶，其特征在于，所述有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二甲基亚砜中的至少一种，和/或，所述催化剂为二月桂酸二丁基锡催化剂。
  9. 根据权利要求1-8中任一项所述的可自愈合气凝胶，其特征在于，所述制备复合水凝胶材料包括以下步骤：
    将复合水凝胶材料的原料混合均匀后，超声混合10-30分钟去除气泡，得到混合液；
    将所述混合液在-50℃-0℃下冷冻10-20h；
    将完成冷冻的混合液在室温下解冻1-5h；
    重复上述冷冻-解冻操作1-5次，得到复合水凝胶材料。
  10. 根据权利要求1-9中任一项所述的可自愈合气凝胶，其特征在于，所述将复合水凝胶材料进行冷冻干燥即得可自愈合气凝胶包括将所述复合水凝胶材料置于压强小于5Pa的真空环境中，于-55℃下冷冻干燥12-48h的步骤。
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CN115011053A (zh) * 2022-06-21 2022-09-06 中国科学院苏州纳米技术与纳米仿生研究所 一种高反射分形结构水凝胶、其制备方法及应用
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CN115011053B (zh) * 2022-06-21 2023-08-01 中国科学院苏州纳米技术与纳米仿生研究所 一种高反射分形结构水凝胶、其制备方法及应用
CN115322502A (zh) * 2022-07-14 2022-11-11 中国科学院上海硅酸盐研究所 一种二氧化硅气凝胶增强聚乙烯醇复合材料及其制备方法
CN115322502B (zh) * 2022-07-14 2023-10-13 中国科学院上海硅酸盐研究所 一种二氧化硅气凝胶增强聚乙烯醇复合材料及其制备方法
CN115197476B (zh) * 2022-07-18 2023-08-22 中国皮革制鞋研究院有限公司 生物基气凝胶及其制备方法和应用
CN115197476A (zh) * 2022-07-18 2022-10-18 中国皮革制鞋研究院有限公司 生物基气凝胶及其制备方法和应用
CN115651393A (zh) * 2022-10-14 2023-01-31 深圳市泰美斯科技有限公司 一种低密度柔性高的导热凝胶及其制备方法
CN115651393B (zh) * 2022-10-14 2023-09-26 深圳市泰美斯科技有限公司 一种低密度柔性高的导热凝胶及其制备方法
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CN119350699A (zh) * 2024-10-24 2025-01-24 上海交通大学 一种生物基水性聚氨酯气凝胶的制备方法与应用
CN119236886A (zh) * 2024-10-31 2025-01-03 深圳晋孚新材料技术有限公司 除臭气凝胶材料及其制造方法
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