WO2024051826A1 - 复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用 - Google Patents

复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用 Download PDF

Info

Publication number
WO2024051826A1
WO2024051826A1 PCT/CN2023/117746 CN2023117746W WO2024051826A1 WO 2024051826 A1 WO2024051826 A1 WO 2024051826A1 CN 2023117746 W CN2023117746 W CN 2023117746W WO 2024051826 A1 WO2024051826 A1 WO 2024051826A1
Authority
WO
WIPO (PCT)
Prior art keywords
phase change
polymer
composite aerogel
composite
aerogel
Prior art date
Application number
PCT/CN2023/117746
Other languages
English (en)
French (fr)
Inventor
郭照琰
李秉海
刘文璐
茹越
姚远
乔金樑
戚桂村
孔德辉
胡晨曦
刘振杰
高易
赖金梅
王湘
张晓红
Original Assignee
中国石油化工股份有限公司
中石化(北京)化工研究院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国石油化工股份有限公司, 中石化(北京)化工研究院有限公司 filed Critical 中国石油化工股份有限公司
Publication of WO2024051826A1 publication Critical patent/WO2024051826A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • 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
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa

Definitions

  • the present invention relates to the field of phase change materials, specifically to a composite aerogel, a recyclable heat storage phase change composite material with photothermal conversion function, and a preparation method and application.
  • phase change materials have large energy storage capacity, near-constant phase change temperature, and reversible storage and release of thermal energy.
  • phase change materials are currently widely used in air conditioning systems, building materials, solar energy storage, waste heat recovery and various electronic products.
  • Organic phase change materials have the advantages of stable performance, low supercooling, and no phase separation.
  • phase change materials are the most widely studied phase change materials and mainly include paraffin, fatty acids, fatty alcohols, and other organic compounds.
  • organic phase change materials will encounter the risk of leakage when directly used as energy storage materials, and it is very necessary to encapsulate phase change materials to prevent leakage problems.
  • organic phase change materials also need to consider reprocessability and recyclability to avoid environmental pollution and resource waste.
  • the purpose of the present invention is to provide a composite aerogel, a recyclable heat storage phase change composite material with a photothermal conversion function, a preparation method and application.
  • the composite aerogel can As a carrier, the phase change material is loaded to obtain a recyclable heat storage phase change composite material with photothermal conversion function, which can also be recycled in a simple and environmentally friendly way; the recyclable heat storage phase with photothermal conversion function
  • the phase change composite material not only has the function of photothermal conversion, but the phase change material has low leakage and can be recycled, truly realizing the use and effective storage of solar energy in an environmentally friendly way.
  • maleimide-based copolymers polymers containing maleic anhydride groups and maleimide groups
  • a composite aerosol of a maleimide-based copolymer and reduced graphene oxide can be prepared by mixing this type of copolymer with graphene oxide and a reducing agent.
  • Glue preferably, water-resistant maleimide-based copolymer graphene composite aerogel can be obtained by quickly and efficiently reducing the aerogel through microwaves.
  • the composite aerogel can be used as a carrier of phase change materials, can be used to prevent leakage of phase change materials, and can be recycled under the action of ammonia water to obtain graphene, phase change materials and polymers respectively.
  • the present invention is intended to realize the leakage prevention and recycling of phase change materials with photothermal conversion function, provide a composite aerogel suitable for phase change material carrier, and a recyclable aerogel with photothermal conversion function. Heat storage phase change composite materials and their preparation methods and applications.
  • a first aspect of the present invention is to provide a composite aerogel, which contains a polymer and graphene, and the polymer contains a structural unit containing a maleic anhydride group and a maleimide-containing structural unit of the group.
  • the composite aerogel can be used as a carrier, and together with the phase change material, a recyclable heat storage phase change composite material with photothermal conversion function can be obtained. At the same time, it can also be recycled in a simple and environmentally friendly way.
  • the average Raman spectrum I D / IG of the surface of the composite aerogel is less than or equal to 1.2, preferably less than or equal to 0.9, and more preferably less than or equal to 0.85.
  • the mass ratio of graphene to polymer can be selected within a wide range.
  • the mass ratio of graphene to polymer is (1:20)-(10: 1), preferably (1:10)-(6:1), more preferably (1:5)-(1:1), that is, 1: (1-5).
  • it can be the ratio of 1 to 1, 2, 3, 4, 5, any two values, or any interval between any two values.
  • the polymer in the composite airgel can be dissolved in ammonia water at 0-150°C to form a polymer aqueous solution.
  • graphene comes from the reduction of graphene oxide.
  • the graphene oxide needs to be pre-reduced using a reducing agent first, and then Microwave reduction. That is, the graphene is obtained by reducing graphene oxide.
  • graphene oxide is first pre-reduced with a reducing agent and then reduced by microwave.
  • the reducing agent can be selected within a wide range.
  • the reducing agent is selected from at least one of ascorbic acid, gallic acid, sodium borohydride, and amino acids.
  • the maleic anhydride group refers to The maleimide group refers to
  • the polymer is a carbon chain polymer in which heteroatoms O and N are present in the pendant groups.
  • the polymer contains male
  • the molar proportion of the structural units of the imide group is 5%-70%, preferably 10%-60%; more preferably 20%-50%, such as 20%, 25%, 30%, 35%, 40% , 45%, 50%, and any two values or any interval between any two values.
  • the polymer can be selected within a wide range.
  • the polymer is derived from a polymer containing maleic anhydride, maleimide, maleic acid and One or more polymer raw materials among the structural units of ammonium salt, maleamic acid and ammonium salt group; that is, the maleic anhydride group and maleimide group in the above-mentioned polymer aerogel are derived At least one of maleic anhydride groups, maleimide groups, maleic acid and ammonium salt groups, maleamic acid and ammonium salt groups in the polymer raw material.
  • the maleic anhydride group refers to The maleimide group refers to Maleic acid and ammonium salt groups, maleamic acid and ammonium salt groups refer to In the formula, M is the same or different, and each is hydroxyl, amino or ammonium (O-NH 4 ).
  • the polymer is a carbon chain polymer in which heteroatoms O and N are present in the pendant groups.
  • the polymer raw materials include but are not limited to one or more polymerized monomers selected from the group consisting of maleic anhydride, maleimide, maleic acid and ammonium salt, maleamic acid and ammonium salt, and Copolymers of olefin monomers; for example, the invention may also be practiced when the polymer starting material is, for example, styrene maleic anhydride vinyl silicone oil copolymer.
  • the copolymers of the above polymerized monomers and olefin monomers including one or more of maleic anhydride, maleimide, maleic acid and ammonium salt, maleamic acid and ammonium salt have lower raw material costs. .
  • the polymer raw material is a polymerized monomer including one or more of maleic anhydride, maleimide, maleic acid and ammonium salt, maleamic acid and ammonium salt, and olefin monomer.
  • Copolymer more preferably, the olefin monomer is at least one of ⁇ -methylstyrene, styrene, and isobutylene; more preferably, the polymer raw material includes maleic anhydride and maleimide Alternating copolymers of one or more polymerized monomers of maleic acid and ammonium salts, maleamic acid and ammonium salts, and one of ⁇ -methylstyrene, styrene, and isobutylene.
  • the polymer raw materials in the present invention include, but are not limited to, at least one of styrene maleic anhydride copolymer and maleic anhydride isobutylene copolymer.
  • the polymer raw material is styrene maleic anhydride copolymer.
  • the composite aerogel can be dissolved in ammonia water at 0-150°C to form a polymer aqueous solution. Based on this, the polymer aerogel of the present invention can be implemented conveniently and environmentally Now for recycling.
  • the polymer in the composite aerogel has good heat resistance and still has good heat resistance after recycling, and is very suitable for photothermal conversion heat storage carrier.
  • the composite aerogel is formed by combining structural units containing maleic anhydride, maleimide, maleic acid and ammonium salt, maleamic acid and ammonium salt groups.
  • One or more of the polymer raw materials react with ammonia water in a closed condition, and then mixed with graphene oxide and a reducing agent, and are prepared after pre-freezing, freeze-drying, dehydration, deamination, and reduction.
  • the second aspect of the present invention is to provide a method for preparing the composite aerogel described in the first aspect, which includes preparing a compound containing maleic anhydride, maleimide, maleic acid, ammonium salt, and maleamide.
  • One or more of the polymer raw materials of the structural units of acid and ammonium salt groups react with ammonia water in a closed condition, and then mixed with graphene oxide and reducing agent, and then undergo pre-freezing, freeze-drying, dehydration and deamination , reduction treatment to obtain the composite aerogel.
  • the preparation method includes the following steps:
  • step (2) Mix the polymer aqueous solution obtained in step (1) with graphene oxide and a reducing agent to obtain a mixed liquid, and then pre-freeze the mixed liquid and then freeze-dry to obtain a composite polymer;
  • step (3) The composite polymer obtained in step (2) is heat treated for dehydration and deamination, and then subjected to microwave irradiation for reduction treatment to obtain the maleimide copolymer graphene composite aerogel.
  • the amount of polymer raw materials, ammonia water, etc. in step (1) can be selected within a wide range.
  • the polymer The mass fraction of the amount of raw materials is 0.1%-30%, preferably 0.5%-10%, more preferably 1%-5%.
  • the mass fraction of the amount of ammonia in the raw materials is 0.001%-30%. , preferably 0.01%-10%, more preferably 0.1%-1%, and the remaining components are water.
  • the reaction conditions in step (1) can be selected within a wide range.
  • the reaction conditions include: reaction temperature is 0-200°C, preferably 50-150°C, more preferably 80-100°C, and/or reaction time is 0.01-100h, preferably It is 0.5-10h, more preferably 1-5h.
  • the reaction pressure is not particularly limited, but it is preferably carried out under normal pressure.
  • the conditions in step (2) can be selected within a wide range.
  • the graphene oxide is derived from a dispersed mixture containing graphene oxide. liquid, the concentration of graphene oxide in the dispersion liquid (that is, the mass ratio of graphene oxide to water) is 1-100 mg/mL, preferably 3-30 mg/mL, and more preferably 5-20 mg/mL.
  • the reducing agent can be selected within a wide range.
  • the reducing agent is selected from at least one of ascorbic acid, gallic acid, sodium borohydride, and amino acids.
  • the mass ratio of the reducing agent to graphene oxide can be selected within a wide range.
  • the mass ratio of the reducing agent to graphene oxide is 1: ( 0.1-20), preferably 1:(1-3), for example, it can be the ratio of 1 to 1, 1.5, 2, 2.5, 3, or any two values or any interval between any two values.
  • the polymer aerogel in the present invention can be an anisotropic aerogel or an isotropic aerogel.
  • anisotropic aerogel The difference between anisotropic aerogel and isotropic aerogel is that the pore structure is different.
  • the aerogel pore structure of anisotropic aerogel shows long-range order, mainly due to the directional growth of ice crystals in the pre-freezing stage of the aerogel. Impurities are discharged during the growth process, and the impurities gather to form the pore wall. Therefore, anisotropic aerogels can be obtained by varying the temperature of the unidirectional cold source during pre-freezing.
  • the one-way cold source temperature including but not limited to using liquid nitrogen as the low-temperature cold source during pre-freezing, and placing a mold containing a mixture of polymer aqueous solution, graphene oxide, and reducing agent.
  • Anisotropic aerogels have different airgel pore structures, different axial and radial thermal conductivity coefficients, and different material and sound transmission rates.
  • Anisotropic aerogels/isotropic aerogels can be selected according to different application situations. glue. For example, when the phase change material is packaged in the present invention, the inventor of the present invention found that using excellent The selected anisotropic aerogel can significantly reduce leakage, and there is no requirement for the direction of the anisotropic aerogel.
  • the cold source temperatures in all directions of the mixed liquid during pre-freezing are the same or different.
  • the cold source temperatures in all directions of the mixed liquid during pre-freezing are different.
  • the mixed solution that is, the mixed aqueous solution of the copolymer obtained after the amination reaction, graphene and the reducing agent
  • the leakage of the phase change material is lower.
  • anisotropic aerogels can be obtained by using different temperatures of the unidirectional cold source during pre-freezing.
  • the one-way cold source temperature including but not limited to when pre-freezing, using liquid nitrogen as the low-temperature cold source, placing the mold on a copper pillar immersed in liquid nitrogen, and ice crystals grow upward from the bottom of the mold. implementation.
  • the pre-freezing conditions can be conventional temperature conditions in the field.
  • the present invention is not particularly limited, as long as the mixture of the polymer aqueous solution, graphene oxide, and reducing agent in step (2) is frozen into ice.
  • the freeze-drying conditions can be selected within a wide range, and the present invention is not particularly limited.
  • the freeze-drying conditions include: the temperature is (-10)°C or below, For example, it may be (-20)°C or lower, or it may be (-30)°C or lower, and/or the vacuum degree may be 1000 Pa or lower, for example, it may be 100 Pa or lower, or it may be 10 Pa or lower.
  • the freeze-drying process can use various freeze-drying equipment in the existing technology, such as freeze dryers, freeze spray dryers, industrial freeze dryers, etc.
  • the conditions in step (3) can be selected within a wide range.
  • the heat treatment conditions include: the temperature is 100-300°C, preferably The temperature is 120-220°C, more preferably 160-200°C; the heat treatment time is 0.1-10 hours, preferably 0.5-3 hours, more preferably 1-2 hours.
  • the conditions of microwave irradiation can be selected within a wide range.
  • the microwave irradiation power is 500-2000W; the microwave irradiation time is 1-10s, preferably 2 -7s, more preferably 3-5s.
  • the polymer raw material can be selected within a wide range.
  • the polymer raw material can react with ammonia water to obtain a water-soluble polymer.
  • the polymer raw material is a structural unit containing maleic anhydride, maleimide, maleic acid and ammonium salt, maleamic acid and ammonium salt groups.
  • One or more polymers preferably, the polymer raw material is one or more of maleic anhydride, maleimide, maleic acid and ammonium salt, maleamic acid and ammonium salt
  • a copolymer of a polymerized monomer and an olefin monomer more preferably, the olefin monomer includes at least one of ⁇ -methylstyrene, styrene, and isobutylene; as an example, the polymer raw materials include but are not It is limited to at least one of styrene maleic anhydride copolymer and maleic anhydride isobutylene copolymer.
  • the above-mentioned polymer raw materials are polymers that have been disclosed in the prior art, and can be commercially available from the prior art, or prepared according to methods disclosed in the prior art.
  • the material of the sealed container is not particularly limited, and it can be a metal, non-metal, polymer or other material container.
  • the "and/or" involved in the present invention means that one of the two conditions before and after "and/or" can be selected, or the two conditions can coexist.
  • the third aspect of the present invention is to provide a recyclable heat storage phase change composite material, which contains a composite aerogel and a phase change material loaded in the composite aerogel; the composite aerogel is the first The composite aerogel described in the first aspect or the composite aerogel prepared by the preparation method described in the second aspect.
  • the mass ratio of the composite aerogel to the phase change material can be selected within a wide range.
  • the mass ratio of the composite aerogel to the phase change material is The mass ratio of the material is 1: (0.05-50).
  • it can be 1 and 0.05, 0.1, 0.5, 1, 5, 10, 20, 30, 40, 50, and any two values or any interval between any two values. Ratio.
  • the phase change material can be selected within a wide range.
  • the phase change material is preferably an organic phase change material, preferably a heat storage phase change material; including but not limited to water-soluble phase change materials and/or
  • the water-insoluble phase change material is more preferably at least one of polyethylene glycol, lauric acid, stearyl alcohol, and paraffin.
  • the leakage amount of the phase change material in the recyclable heat storage phase change composite material is less than 10wt%, preferably less than 5wt%, and more preferably less than 2wt%.
  • the invention also provides a recycling method of composite aerogel or recyclable heat storage phase change composite material.
  • the recycling method includes combining the composite aerogel and/or recyclable heat storage phase change composite material with ammonia water under closed conditions. Mix and react until an aqueous solution containing the recycled polymer is obtained. Insoluble matter (graphene, phase change material) is removed to obtain an aqueous solution of the recycled polymer.
  • This airgel recycling method does not require the introduction of organic solvents, and does not require high-temperature and high-pressure stirring. It only requires a certain concentration of ammonia water, preferably kept below 100 degrees Celsius, and can achieve rapid and efficient recycling. This method has low energy consumption, little pollution, high efficiency, and the recovered The polymer solution can again be used in the preparation of polymer aerogels.
  • the conditions of the mixing reaction in the recovery method can be selected within a wide range.
  • the temperature of the mixing reaction is 0-200°C, preferably 50-150°C, and more preferably The temperature is 80-100°C, and/or the mixing reaction time is 0.01-100h, preferably 0.5-10h, more preferably 1-5h.
  • the reaction pressure is not particularly limited, but it is preferably carried out under normal pressure.
  • the recycling method also includes reusing the aqueous solution of the recycled polymer, for example, continuing step (2) and subsequent steps in the preparation method described in the second aspect of the present invention. Steps to prepare composite aerogel again.
  • a fourth aspect of the present invention is to provide a method for preparing the recyclable heat storage phase change composite material described in the third aspect, including loading the phase change material in the composite aerogel.
  • the preparation method of the recyclable heat storage phase change composite material includes: adopting the preparation method described in the second aspect to obtain a composite aerogel; loading the phase change material in the composite aerogel in gel.
  • the load mode may be various load modes existing in the prior art. Specifically, the phase change material may be in a molten state and then adsorbed (encapsulated) and/or penetrated into the composite aerogel.
  • the type and ratio of the phase change material can be selected within a wide range, and the type and ratio of the phase change material described in the third aspect of the invention are preferably selected.
  • the fifth aspect of the present invention is to provide a recyclable heat storage phase change composite material according to the fourth aspect.
  • the present invention provides a composite aerogel, a recyclable heat storage phase change composite material with photothermal conversion function, and a preparation method and application thereof. Compared with the existing technology, the present invention has the following advantages:
  • the composite aerogel in the present invention is used as a carrier, and the graphene in it endows the phase change material with a photothermal conversion function.
  • the aerogel phase change composite material containing graphene can be heated to above 70°C within 30 minutes under sunlight irradiation. It can keep the temperature above 50°C for a long time and has good photothermal conversion performance and heat storage performance.
  • the recyclable heat storage phase change composite material with photothermal conversion function in the present invention can realize efficient utilization of solar energy.
  • the composite aerogel and recyclable heat storage phase change composite material with photothermal conversion function in the present invention can be recycled in a green and environmentally friendly manner;
  • the polymers in the composite aerogel and the recycled polymers have good heat resistance.
  • the porous structure of the composite aerogel enables low leakage of phase change materials. All of the above are provided by photothermal conversion and heat storage. Stability is guaranteed.
  • the recyclable heat storage phase change composite material with photothermal conversion function in the present invention not only has a photothermal conversion function, but also has good heat storage performance, and the phase change material leakage is low and the overall
  • the materials can be recycled, truly realizing the use of solar energy in an environmentally friendly way and effectively storing it, which has extremely high application value in the environmentally friendly use of clean energy.
  • Figure 1 is the DSC curve and glass transition temperature Tg of the maleimide-based aerogel in Comparative Example 1 and the polymer aerogel recovered in Example 4;
  • Figure 2 is the thermal weight loss curve of the maleimide-based aerogel in Comparative Example 1 and the polymer aerogel recovered in Example 4;
  • test results in Figures 1 and 2 show that maleimide-based aerogels have good heat resistance, with a glass transition temperature near 250°C and a decomposition temperature around 300°C.
  • the airgel prepared by recycling the polymer The heat resistance of the gel is higher than that before recycling, which proves that the polymer has good heat resistance before and after recycling the airgel, and the recycling process is green and environmentally friendly.
  • Figure 3 is a curve of the phase change material of Example 2 and Example 5 at a solar illumination intensity and removing illumination temperature.
  • FIG 4 shows the maleimide-based copolymer graphene aerogel phase change composite material (a) obtained in Example 2 of the recycling process and the graphene phase change composite material (b) and polymer aerogel obtained after recycling. (c), the above is described in Example 4. It can be seen that the materials in the recyclable heat storage phase change composite material with photothermal conversion function in the present invention can be separately recycled and reused.
  • Thermogravimetric analysis (TGA, Mettler Toledo, Switzerland) was used to determine the thermal stability of the sample, and 5 mg of aerogel was taken for testing. The test was conducted under nitrogen flow, with a heating rate of 20°C/min and a temperature range of From 50°C to 550°C.
  • the glass transition temperature of the samples was measured using a Perkin-Elmer pyris -1 differential scanning calorimeter (DSC), calibrated using indium and zinc standards. 5-6mg sample from the injection rod was heated from 150°C to 300°C under nitrogen flow and held at 300°C for 3 minutes. Next, the sample was cooled to 150°C for 1 min and heated again to 300°C. All heating and cooling processes are programmed at a speed of 10°C/min. The glass transition temperature (Tg) was determined based on the relevant peaks in the DSC curve.
  • DSC Perkin-Elmer pyris -1 differential scanning calorimeter
  • phase change material was cut into 3cm*3cm*0.3cm sheets as test samples, and sunlight simulator Sirius-SS300A-D produced by Beijing Zhuoli Hanguang Instrument Co., Ltd. was used to simulate sunlight at 20 degrees Celsius.
  • the sample was placed in a polystyrene foam box without a lid, and the temperature changes of the phase change composite were monitored throughout with a thermocouple. First, irradiate for about 34 minutes under a light intensity of 100mW/cm 2 (one solar light intensity), and then turn off the simulated light source.
  • the leakage amount is: m/15*100wt% , if the sample is completely melted and cannot be removed, the leakage amount is 100wt%.
  • Thermal properties of aerogels and phase change materials were measured using differential scanning calorimetry (DSC) using a Perkin-Elmer pyris-1 calibrated with indium and zinc standards.
  • DSC differential scanning calorimetry
  • the samples were heated from 20 to 150°C under nitrogen flow and held at 20°C and 150°C for 5 min respectively.
  • phase change materials the samples were heated from 50°C to 300°C under nitrogen flow and stored at 50°C and 300°C for 5 min respectively. All heating and cooling processes are programmed at a speed of 20°C/min.
  • the latent heat of melting ⁇ Hm and the latent heat of solidification ⁇ Hf as well as the melting temperature Tm and solidification temperature Tf are determined according to the relevant peaks of the DSC curve.
  • the polymer is prepared as follows: 500 ml of isoamyl acetate is placed in a 1000 ml three-necked flask, nitrogen is introduced for 30 minutes to remove oxygen, and 24.5 g of maleic anhydride and 26 g of styrene are added to the flask. After it is completely dissolved, add 0.4g of azobisisobutyronitrile, raise the temperature of the water bath to 70°C, and react for 7 hours.
  • the aerogel was placed in a polytetrafluoroethylene liner filled with nitrogen, and placed in a 180°C constant temperature oven for heat treatment for 2 hours.
  • the sample was taken out and placed in a sealed quartz jar filled with nitrogen, and then microwaved (irradiation power was 800W) for 3 seconds to obtain a maleimide styrene copolymer graphene composite aerogel (ie, the composite aerogel in the present invention).
  • maleimide graphene composite aerogel Prepare maleimide graphene composite aerogel according to the method in Example 1. Place 0.2g maleimide graphene composite aerogel into a polytetrafluoroethylene beaker containing 20g sliced paraffin, and place the container After being placed in a vacuum oven and kept at 100°C for 2 hours, the molten paraffin penetrated into the maleimide graphene composite aerogel, thereby obtaining an airgel phase change composite material; the airgel phase change composite material Take it out from the container, and then wipe away the excess phase change material on the surface of the airgel phase change composite. After leaving it at room temperature for 2 hours, weigh it to obtain the maleimide-based copolymer graphene airgel phase change composite. (Absorbed paraffin wax is about 10g).
  • Example 2 The phase change material in Example 2 was replaced from paraffin with stearyl alcohol (purchased from Aladdin), and the remaining experiments were consistent with Example 2.
  • phase change composite material recycling effect is close to that of Example 2.
  • Example 2 Grind the phase change composite material sample obtained in Example 2 into powder, take 5g of the powder, and place it on a cover glass into a glass bottle, then add 0.2g of 25% ammonia and 30ml of water, heat to 95°C and maintain for 1 hour under magnetic stirring at 1000r/min, then filter while hot (a in Figure 4), and the filtrate is heated After concentrating to about 5 ml, place it in the mold refrigerator to pre-freeze, then place it in a freeze dryer to freeze dry (temperature below -30°C, pressure below 10 Pa) to obtain the recovered polymer aerogel (c in Figure 4). After the filter cake is naturally dried, it is placed in a small beaker, heated to 100°C and melted for 1 hour.
  • Example 1 The microwave treatment time in Example 1 was changed to 1 s, and other preparation steps were the same as Example 1.
  • the aerogel was placed in a polytetrafluoroethylene liner filled with nitrogen, and placed in a 180°C constant temperature oven for heat treatment for 2 hours.
  • the sample was taken out and placed in a sealed quartz jar filled with nitrogen, and then microwaved (irradiation power was 800W) for 5s to obtain maleimide styrene copolymer graphene composite aerogel.
  • the aerogel was placed in a polytetrafluoroethylene liner filled with nitrogen, and placed in a 180°C constant temperature oven for heat treatment for 2 hours.
  • the sample was taken out and placed in a sealed quartz jar filled with nitrogen, and then microwaved (irradiation power was 800W) 7s to obtain maleimide styrene copolymer graphene composite aerogel.
  • reaction kettle Take a reaction kettle with a polytetrafluoroethylene inner tank, add 20.5g of water, then add 4g of 25% ammonia water and 0.5g of maleic anhydride-styrene copolymer, and put the reaction kettle into an oven to maintain 150°C. , take it out after 10 hours to obtain a uniform polymer solution.
  • the aerogel was placed in a polytetrafluoroethylene liner filled with nitrogen, and placed in a 200°C incubator for heat treatment for 2 hours.
  • the sample was taken out and placed in a closed quartz jar filled with nitrogen, and then microwaved (irradiation power was 500W) for 3s to obtain maleimide styrene copolymer graphene composite aerogel.
  • the aerogel was placed in a polytetrafluoroethylene liner filled with nitrogen and placed in a 130°C constant temperature oven for heat treatment for 2 hours.
  • the sample was taken out and placed in a closed quartz jar filled with nitrogen, and then microwaved (irradiation power was 2000W)3s to obtain maleimide styrene copolymer graphene composite aerogel.
  • phase change temperature and phase change latent heat are close to those in Example 2.
  • paraffin phase change material ie, pure phase change material
  • Example 1 and Examples 6-8 The ID/IG test results of the aerogels prepared in Example 1 and Examples 6-8 are listed in Table 1, and the leakage conditions of the phase change materials prepared in Example 2, Comparative Example 2 and Example 5 are listed in Table 2; Comparison The DSC curves and glass transition temperatures Tg of Examples 1 and 4 are shown in Figure 1; the thermogravimetric curves of Comparative Examples 1 and 4 are shown in Figure 2; the phase change materials of Examples 2 and 5 were exposed on a solar The light intensity and light removal temperature curves are shown in Figure 3.
  • the test results in Figure 3 show that graphene gives phase change materials the photothermal conversion function.
  • the airgel phase change composite material containing graphene can be heated to above 70°C within 30 minutes and can maintain the temperature above 50°C for a long time. , has good photothermal conversion performance and can achieve efficient utilization of solar energy.
  • the composite phase change material in Example 6 was tested according to the same method. Compared with Example 2, the photothermal conversion performance of the composite phase change material in Example 2 is better than that in Example 6.
  • test results in Table 1 show that the composite airgel prepared by the present invention has a very high reduction efficiency and can reach a high degree of reduction in 3 seconds, which is conducive to rapid and large-scale industrial preparation.
  • any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of the present invention and shall not It should be regarded as new content that has not been disclosed or expected herein, unless those skilled in the art believe that the combination is obviously unreasonable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及相变材料领域，具体是涉及一种复合气凝胶、具有光热转化功能的可回收储热相变复合材料及其制备方法和应用。该复合气凝胶含有聚合物和石墨烯，所述聚合物中含有含马来酸酐基团的结构单元和含马来酰亚胺基团的结构单元。该复合气凝胶可以作为载体，负载相变材料从而得到具有光热转化功能的可回收储热相变复合材料，同时还可以通过简单环保地方式回收。该可回收储热相变复合材料，含有复合气凝胶和负载于所述复合气凝胶中的相变材料。本发明中的具有光热转化功能的可回收储热相变复合材料不仅具有光热转化功能，而且相变材料泄漏量低同时又可以回收，真正实现环保方式利用太阳能并有效储存，在清洁能源的环保利用方面具有极高的应用价值。

Description

复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用 技术领域
本发明涉及相变材料领域，具体是涉及一种复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用。
背景技术
随着能源消耗和温室气体排放的迅速增加，以环保方式利用太阳能和废热等可再生能源具有极大的吸引力。由于太阳能会随着时间和空间变化，能源供需的不匹配使得这些能源的有效储存成为一个重要问题。基于有机相变材料的潜热储能系统具有大储能容量、接近恒定的相变温度和可逆的储存和释放热能。通过相变材料，可以弥合快速增长的能源需求与有限的化石资源储量之间的巨大差距。因此，相变材料目前广泛用于空调系统、建筑材料、太阳能储存、废热回收和各种电子产品。有机相变材料具有性能稳定、过冷度低、无相分离等优点，是研究最为广泛的相变材料，主要包括石蜡、脂肪酸、脂肪醇以及其他有机化合物。然而，有机相变材料在直接用作储能材料时会遇到泄漏的风险，对相变材料进行封装以防止泄漏问题是非常必要的。此外，有机相变材料还需要考虑可再加工性和可回收性，避免其造成环境污染和资源浪费。
因此，若提供一种具有光热转化性能的材料，结合相变材料得到具有良好的光热转化性能、相变材料泄漏量低同时又可以回收的可回收蓄冷相变复合材料，将在本领域实现大的突破。
发明内容
针对现有技术中存在的技术问题，本发明的目的是提供一种复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用，该复合气凝胶可 以作为载体，负载相变材料从而得到具有光热转化功能的可回收储热相变复合材料，同时还可以通过简单环保地方式回收；所述具有光热转化功能的可回收储热相变复合材料不仅具有光热转化功能，而且相变材料泄漏量低同时又可以回收，真正实现以环保方式利用太阳能并有效储存。
本发明的发明人发现，马来酰亚胺基共聚物(含有马来酸酐基团和马来酰亚胺基团的聚合物)可以通过低成本的共聚物制备，并且可以通过氨水进行回收。针对现有技术，本发明申请人在研究中发现，将此类共聚物与氧化石墨烯和还原剂混合经制备，可制得马来酰亚胺基共聚物和还原氧化石墨烯的复合气凝胶；优选地，将气凝胶通过微波进行快速高效还原，可以得到耐水的马来酰亚胺基共聚物石墨烯复合气凝胶。该复合气凝胶可以作为相变材料的载体，可用于相变材料的防泄漏，并且在氨水的作用下可以进行回收，分别得到石墨烯、相变材料和聚合物。综上所述，本发明意在实现具有光热转化功能的相变材料的防泄漏与回收，提供一种适用于相变材料载体的复合气凝胶，以及具有光热转化功能的可回收储热相变复合材料及其制备方法和应用。
本发明的第一个方面是提供一种复合气凝胶，该复合气凝胶含有聚合物和石墨烯，所述聚合物中含有含马来酸酐基团的结构单元和含马来酰亚胺基团的结构单元。该复合气凝胶可以作为载体，与相变材料一起得到具有光热转化功能的可回收储热相变复合材料，同时还可以通过简单环保地方式回收。
在本发明一种优选的实施方式中，所述复合气凝胶表面的拉曼光谱ID/IG平均值小于等于1.2，优选小于等于0.9，更优选小于等于0.85。
根据本发明，石墨烯与聚合物的质量比可以在较宽的范围内选择，在本发明一种优选的实施方式中，石墨烯与聚合物的质量比为(1：20)-(10：1)，优选为(1：10)-(6:1)，更优选(1：5)-(1：1)，也即1：(1-5)。例如可以为1与1、2、3、4、5以及任意两数值或者任意两数值的任意区间之比。
根据本发明，所述复合气凝胶中的聚合物能够溶于0-150℃的氨水中，形成聚合物水溶液。
在本发明一种优选的实施方式中，制备本发明所述的复合气凝胶的原材料中，石墨烯来自于对氧化石墨烯的还原，氧化石墨烯需先使用还原剂进行预还原，再进行微波还原。即所述石墨烯通过将氧化石墨烯还原后得到，优选将氧化石墨烯先用还原剂进行预还原，再进行微波还原后得到。
根据本发明，所述还原剂可以在较宽的范围内选择，在本发明一种优选的实施方式中，所述还原剂选自抗坏血酸、没食子酸、硼氢化钠、氨基酸中的至少一种。
根据本发明，马来酸酐基团指的是马来酰亚胺基团指的是
根据本发明，所述聚合物是碳链聚合物，其中杂原子O和N存在于侧基中。
在本发明一种优选的实施方式中，以含马来酸酐基团的结构单元和含马来酰亚胺基团的结构单元的总摩尔量为100％计，所述聚合物中含马来酰亚胺基团的结构单元的摩尔比例为5％-70％，优选为10％-60％；更优选为20％-50％，例如20％、25％、30％、35％、40％、45％、50％，以及任意两数值或者任意两数值的任意区间。
根据本发明，所述聚合物可以在较宽的范围内选择，在本发明一种优选的实施方式中，所述聚合物衍生自含有含马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐基团的结构单元中的一种或几种的聚合物原料；即上述聚合物气凝胶中的马来酸酐基团和马来酰亚胺基团衍生自所述聚合物原料中的马来酸酐基团、马来酰亚胺基团、马来酸及铵盐基团、马来酰胺酸及铵盐基团中的至少一种。
马来酸酐基团指的是马来酰亚胺基团指的是马来酸及铵盐基团、马来酰胺酸及铵盐基团指的是式中M相同或不同，各自为羟基或氨基或铵(O-NH4)。
根据本发明，所述聚合物是碳链聚合物，其中杂原子O和N存在于侧基中。
本发明中，所述聚合物原料包括但不限于包括马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐中的一种或几种的聚合单体与烯烃单体的共聚物；例如，当所述聚合物原料为诸如苯乙烯马来酸酐乙烯基硅油共聚物时，也可以实现本发明。以上包括马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐中的一种或几种的聚合单体与烯烃单体的共聚物具有更低的原料成本。
优选地，所述聚合物原料为包括马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐中的一种或几种的聚合单体与烯烃单体的共聚物；更优选地，所述烯烃单体为α-甲基苯乙烯、苯乙烯、异丁烯中的至少一种；更优选地，所述聚合物原料为包括马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐中的一种或几种的聚合单体与α-甲基苯乙烯、苯乙烯、异丁烯中的一种的交替共聚物。
作为举例，本发明中所述聚合物原料包括但不限于苯乙烯马来酸酐共聚物、马来酸酐异丁烯共聚物中的至少一种。优选地，所述聚合物原料为苯乙烯马来酸酐共聚物。
在本发明一种优选的实施方式中，所述复合气凝胶能够溶于0-150℃的氨水中，形成聚合物水溶液。基于此，本发明的聚合物气凝胶能够方便环保地实 现回收利用。
根据，本发明中的复合气凝胶中的聚合物具有很好的耐热性，并在回收后依然具有很好的耐热性能，非常适用于光热转变储热载体。
在本发明一种优选的实施方式中，所述复合气凝胶通过将含有含马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐基团的结构单元中的一种或几种的聚合物原料与氨水在密闭情况下发生反应，再与氧化石墨烯、还原剂混合后，经预冷冻、冷冻干燥、脱水脱氨、还原处理后制备得到。
本发明的第二个方面是提供一种第一个方面所述的复合气凝胶的制备方法，包括将含有含马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐基团的结构单元中的一种或几种的聚合物原料与氨水在密闭情况下发生反应，再与氧化石墨烯、还原剂混合后，经预冷冻、冷冻干燥、脱水脱氨、还原处理，得到所述复合气凝胶。
本发明的复合气凝胶制备方法中不加入交联剂。
在本发明一种优选的实施方式中，所述制备方法包括以下步骤：
(1)将所述聚合物原料与氨水在密闭情况下发生反应，得到聚合物水溶液；
(2)将步骤(1)得到的聚合物水溶液与氧化石墨烯、还原剂混合得到混合液，之后将混合液进行预冷冻，再经冷冻干燥，得到复合聚合物；
(3)将步骤(2)得到的复合聚合物进行热处理来脱水脱氨，之后进行微波辐照来还原处理，得到所述马来酰亚胺共聚物石墨烯复合气凝胶。
根据本发明，步骤(1)中聚合物原料、氨水的用量等可以在较宽的范围内选择，在本发明一种优选的实施方式中，以反应体系的总质量为100％计，聚合物原料用量的质量分数为0.1％-30％，优选为0.5％-10％，更优选为1％-5％，以氨水中氨的质量计，原料中氨用量的质量分数为0.001％-30％，优选为0.01％-10％，更优选为0.1％-1％，其余组分为水。
根据本发明，步骤(1)中的反应的条件等可以在较宽的范围内选择，在 本发明一种优选的实施方式中，反应的条件包括：反应温度为0-200℃，优选为50-150℃，更优选为80-100℃，和/或，反应时间为0.01-100h，优选为0.5-10h，更优选为1-5h。反应压力没有特殊限定，优选常压下进行。
根据本发明，步骤(2)中的条件可以在较宽的范围内选择，在本发明一种优选的实施方式中，步骤(2)中：所述氧化石墨烯来源于含有氧化石墨烯的分散液，分散液中氧化石墨烯的浓度(也即氧化石墨烯与水的质量比)为1-100mg/mL，优选为3-30mg/mL，更优选5-20mg/mL。
根据本发明，所述还原剂可以在较宽的范围内选择，在本发明一种优选的实施方式中，所述还原剂选自抗坏血酸、没食子酸、硼氢化钠、氨基酸中的至少一种。
根据本发明，所述还原剂与氧化石墨烯的质量比可以在较宽的范围内选择，在本发明一种优选的实施方式中，所述还原剂与氧化石墨烯的质量比为1：(0.1-20)，优选为1:(1-3)，例如可以为1与1、1.5、2、2.5、3，以及任意两数值或者任意两数值的任意区间之比。
根据本发明，本发明中的聚合物气凝胶可以为各向异性气凝胶，也可以为各向同性气凝胶。
各向异性气凝胶与各向同性气凝胶区别是孔结构不同，各向异性气凝胶的气凝胶孔结构表现出长程有序，主要在于气凝胶在预冷冻阶段冰晶定向生长，生长过程中将杂质排出，杂质聚集即形成孔壁。因此，预冷冻时单向冷源温度不同可以得到各向异性气凝胶。单向冷源温度的实施方式可以有多种选择，包括但不限于在预冷冻时，以液氮为低温冷源，将装盛聚合物水溶液与氧化石墨烯、还原剂的混合液的模具放在浸入液氮的铜柱上，冰晶从模具底部向上生长，这样的实施方式。
各向异性气凝胶中气凝胶孔结构不同，轴向径向的导热系数不同，物质和声音传输速率也不同，可以根据不同的应用情况选取各向异性气凝胶/各向同性气凝胶。例如，在本发明中相变材料在封装时，本发明的发明人发现，采用优 选的各向异性气凝胶，泄漏量能够明显降低，而对各向异性气凝胶的方向没有要求。
根据本发明，所述预冷冻时混合液的各个方向冷源温度相同或不同，在本发明一种优选的实施方式中，所述预冷冻时混合液的各个方向冷源温度不同，优选地，所述预冷冻时混合液(即胺化反应后所得的共聚物与石墨烯和还原剂的混合水溶液)所处的单向冷源温度不同。在此优选的实施方式中，相变材料的泄漏量更低。
优选预冷冻时单向冷源温度不同可以得到各向异性气凝胶。单向冷源温度的实施方式可以有多种选择，包括但不限于预冷冻时，以液氮为低温冷源，将模具放在浸入液氮的铜柱上，冰晶从模具底部向上生长，这样的实施方式。
具体地，预冷冻的条件可以是本领域的常规的温度条件，本发明没有特别的限制，只要将步骤(2)的聚合物水溶液与氧化石墨烯、还原剂的混合液冷冻成冰即可。
根据本发明，冷冻干燥的条件可以在较宽的范围内选择，本发明没有特别的限制，在本发明一种优选的实施方式中，冷冻干燥的条件包括：温度为(-10)℃以下，例如可以为(-20)℃以下，也可以为(-30)℃以下，和/或，真空度为1000Pa以下，例如可以为100Pa以下，也可以为10Pa以下。
冷冻干燥过程可以采用现有技术中的各种冷冻干燥设备，比如冷冻干燥机，冷冻喷雾干燥机，工业冷冻干燥机等。
根据本发明，步骤(3)中的条件可以在较宽的范围内选择，在本发明一种优选的实施方式中，步骤(3)中：热处理的条件包括：温度为100-300℃，优选为120-220℃，更优选为160-200℃；热处理时间为0.1-10小时，优选为0.5-3小时，更优选为1-2小时。
根据本发明，微波辐照的条件可以在较宽的范围内选择，在本发明一种优选的实施方式中，微波辐照功率为500-2000W；微波辐照时间为1-10s，优选为2-7s，更优选为3-5s。
根据本发明，所述聚合物原料可以在较宽的范围内选择，在本发明一种优选的实施方式中，所述聚合物原料能够与氨水反应得到水溶性聚合物。
在本发明一种优选的实施方式中，所述聚合物原料为含有含马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐基团的结构单元中的一种或几种的聚合物；优选地，所述聚合物原料为包括马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐中的一种或几种的聚合单体与烯烃单体的共聚物；更优选地，所述烯烃单体包括α-甲基苯乙烯、苯乙烯、异丁烯中的至少一种；作为举例，所述聚合物原料包括但不限于苯乙烯马来酸酐共聚物、马来酸酐异丁烯共聚物中的至少一种。
以上所述的聚合物原料均现有技术已经公开的聚合物，可以来自现有技术市售，或根据现有技术所公开的方法来制备。
本发明中对密闭容器的材质没有特别限制，可以为金属、非金属、高分子等材料容器。
本发明涉及的“和/或”指的是“和/或”前后的两种条件可以择一，也可以两种条件并存。
本发明的第三个方面是提供一种可回收储热相变复合材料，含有复合气凝胶和负载于所述复合气凝胶中的相变材料；所述复合气凝胶为第一个方面所述的复合气凝胶或者第二个方面所述的制备方法制备得到的复合气凝胶。
根据本发明，所述复合气凝胶与所述相变材料的质量比可以在较宽的范围内选择，在本发明一种优选的实施方式中，所述复合气凝胶与所述相变材料的质量比为1：(0.05-50)，例如，可以为1与0.05、0.1、0.5、1、5、10、20、30、40、50，以及任意两数值或者任意两数值的任意区间之比。
根据本发明，所述相变材料可以在较宽的范围内选择，所述相变材料优选为有机相变材料，优选为储热相变材料；包括但不限于水溶性相变材料和/或非水溶性相变材料，更优选为聚乙二醇、月桂酸、十八醇、石蜡中的至少一种。
在本发明一种优选的实施方式中，在所述相变材料为液态的温度条件下， 可回收储热相变复合材料中相变材料的泄漏量小于10wt％，优选小于5wt％，更优选小于2wt％。
本发明还提供一种复合气凝胶或可回收储热相变复合材料的回收方法，回收方法包括将复合气凝胶和/或可回收储热相变复合材料与氨水于密闭条件下混合反应，直至得到含有回收聚合物的水溶液，除去不溶物(石墨烯、相变材料)，得到回收聚合物的水溶液。该气凝胶回收方法无需引入有机溶剂，不需要高温高压搅拌处理，只需一定浓度氨水优选保持100摄氏度以下，可实现快速高效回收，该方法能耗低，污染小，效率高，回收得到的聚合物溶液可再次用于聚合物气凝胶的制备。
根据本发明，回收方法中混合反应的条件可以在较宽的范围内选择，在本发明一种优选的实施方式中，混合反应的温度为0-200℃，优选为50-150℃，更优选为80-100℃，和/或，混合反应的时间为0.01-100h，优选为0.5-10h，更优选为1-5h。反应压力没有特殊限定，优选常压下进行。
在本发明一种优选的实施方式中，所述回收方法还包括将回收聚合物的水溶液再次重新利用，例如，延续本发明第二个方面所述的制备方法中的步骤(2)以及后续的步骤，重新制备得到复合气凝胶。
本发明的第四个方面是提供一种第三个方面所述的可回收储热相变复合材料的制备方法，包括将所述相变材料负载在所述复合气凝胶中。
根据本发明，所述可回收储热相变复合材料的制备方法包括：采用第二个方面所述的制备方法，得到的复合气凝胶；将所述相变材料负载在所述复合气凝胶中。所述的负载方式，可以是现有技术中已有的各种负载方式。具体可以是将相变材料处于熔融状态后吸附(封装)和/或渗透于所述的复合气凝胶中。
根据本发明，所述相变材料的种类、配比可以在较宽的范围内选择，优选为本发明中第三个方面所述的相变材料的种类、配比。
本发明的第五个方面是提供一种第四个方面所述的可回收储热相变复合材 料在建筑节能、空调系统、废热利用、太阳能储存领域中的应用。
通过上述技术方案，本发明提供了一种复合气凝胶、具有光热转化功能的可回收储热相变复合材料及其制备方法和应用。与现有技术相比，本发明具有以下优势：
本发明中的复合气凝胶作为载体，其中的石墨烯赋予了相变材料光热转化功能，含有石墨烯的气凝胶相变复合材料可以在太阳光照射下30min内升温至70℃以上，并可长时间保持温度在50℃以上，具有良好的光热转化性能和储热性能。结合相变材料的储热性能，本发明中的具有光热转化功能的可回收储热相变复合材料可以实现对太阳能的高效利用。
本发明中的复合气凝胶、具有光热转化功能的可回收储热相变复合材料可以通过绿色环保的方式进行回收利用；
复合气凝胶中的聚合物以及回收后的聚合物均具有较好的耐热性能，同时，复合气凝胶的多孔结构使得相变材料泄漏量低，以上均为光热转化以及储热提供了稳定性保障。
综上所述，本发明中的具有光热转化功能的可回收储热相变复合材料不仅具有光热转化功能，而且具有较好的储热性能，而且相变材料泄漏量低同时整体的材料又可以回收，真正实现环保方式利用太阳能并有效储存，在清洁能源的环保利用方面具有极高的应用价值。
附图说明
图1是比较例1中的马来酰亚胺基气凝胶和实施例4中回收的聚合物气凝胶的DSC曲线和玻璃化转变温度Tg；
图2是比较例1中的马来酰亚胺基气凝胶和实施例4中回收的聚合物气凝胶的热失重曲线；
图1和图2的测试结果表明，马来酰亚胺基气凝胶耐热性较好，玻璃化转变温度在250℃附近，分解温度在300℃附近，经过回收的聚合物所制备的气 凝胶耐热性要高于回收前的，证明了气凝胶回收前后聚合物均具有良好的耐热性，回收过程绿色环保。
图3是实施例2和实施例5的相变材料在一个太阳光照强度和移除光照温度曲线。
图3的测试结果表明，石墨烯赋予了相变材料光热转化功能，含有石墨烯的气凝胶相变复合材料在模拟太阳光照射下可以在30min内升温至70℃以上，并可长时间保持温度在50℃以上，具有良好的光热转化性能和储热性能，可以实现对太阳能的高效利用。
图4是回收处理实施例2得到的马来酰亚胺基共聚物石墨烯气凝胶相变复合材料(a)和回收后得到的石墨烯相变复合材料(b)以及聚合物气凝胶(c)，以上记载在实施例4中。可见，本发明中的具有光热转化功能的可回收储热相变复合材料中的材料可以分别回收重复利用。
具体实施方式
下面结合具体实施例对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明的进一步说明，不能理解为对本发明保护范围的限制，本领域技术人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属本发明的保护范围。
下面结合实施例，进一步说明本发明；但本发明不受这些实施例的限制。
实施例中的实验数据使用以下仪器及测定方法测定：
1、气凝胶的拉曼光谱ID/IG测试方法：
使用HORIBA JOBIN YVON公司的Lab RAM HR800拉曼光谱仪进行测试，使用机器自带软件处理曲线，并得到ID和IG值。
2、气凝胶的热稳定性测试方法：
采用热重分析(TGA,Mettler Toledo,Switzerland)测定样品的热稳定性，取5mg气凝胶进行测试。测试在氮气流下进行，升温速率为20℃/min，温度范围 从50℃到550℃。
3、气凝胶玻璃化转变温度测试方法：
样品的玻璃化转变温度使用Perkin-Elmer pyris-1差示扫描量热仪(DSC)进行，使用铟和锌标准校准。5-6mg样品来自注射棒，在氮气流下从150℃加热到300℃，在300℃保持3分钟。接下来，样品冷却到150℃1分钟，再次加热到300℃。所有加热和冷却过程的编程速度为10℃/min。根据DSC曲线中的相关峰测定玻璃化转变温度(Tg)。
4、相变材料模拟太阳光照温度变化曲线测试方法：
将相变材料切割为3cm*3cm*0.3cm的片材作为测试样品，在20摄氏度下使用北京卓立汉光仪器有限公司生产的太阳光模拟器Sirius-SS300A-D模拟太阳光照。将样品置于无盖的聚苯乙烯泡沫箱中，并通过热电偶全程监测相变复合材料的温度变化。首先在光照强度为100mW/cm2(一个太阳光照强度)下照射约34分钟后，再关闭模拟光源。
5、相变材料泄漏量测试方法：
取15g实施例所得样品，取滤纸放于120℃加热台上，将样品放于滤纸上10分钟，取下样品，对样品称重得m(g)，泄漏量为:m/15*100wt％，若样品完全融化，无法取下，泄漏量为100wt％。
6、相变温度的测试方法：
采用差示扫描量热法(DSC)测量气凝胶和相变材料的热性能，采用铟和锌标准品校准的Perkin-Elmer pyris-1。对于气凝胶，样品在氮气流下从20-150℃加热，在20℃和150℃分别保持5min。对于相变材料，样品在氮气流下从50℃加热到300℃，分别在50℃和300℃保存5min。所有加热和冷却过程的编程速度为20℃/min。根据DSC曲线的相关峰确定熔融潜热ΔHm和凝固潜热ΔHf以及熔融温度Tm和凝固温度Tf。
实施例中所用的原料描述于表I中。
表I
制备例1
本发明实施例中聚合物制备：将500ml乙酸异戊酯置于1000ml三口烧瓶，通入氮气30min除去氧气，将24.5g马来酸酐和26g苯乙烯加入烧瓶中。待完全溶解后，加入0.4g偶氮二异丁腈，将水浴锅温度升温至70℃，反应7h。反应后在10000r下离心10min，除去上清液，加入500ml甲醇，搅拌0.5小时，离心后去除去上清液，重复两次，然后140℃真空干燥24h，得到苯乙烯马来酸酐共聚物。
实施例1
取93.2g水，将其加入到带盖玻璃瓶中，再加入2.8g质量分数为25％的氨水和4g马来酸酐-苯乙烯共聚物，将玻璃瓶盖旋紧后放入烘箱中保持95℃，4小时后取出得到均一的4％质量分数聚合物溶液。
向玻璃瓶内加入100g 20mg/ml氧化石墨烯水溶液，再加入4g抗坏血酸，1000r/min下磁力搅拌5min，待混合均匀后，迅速将其倒入下底面为铜，壁为聚四氟乙烯的圆柱模具中，并将其放置于液氮浴中的铜柱上。待预冻完成后(即将混合液冷冻成冰后)，放入冷冻干燥机中，(温度为-30℃以下，压力为10Pa以下)冷冻干燥72小时后，得到各向异性的水溶性GO/SMI复合气凝胶。
然后将该气凝胶置于充有氮气的聚四氟乙烯内胆中，放入180℃恒温箱中热处理2h，取出样品放入充有氮气的密闭石英罐中，微波处理(辐照功率为800W)3s得到马来酰亚胺苯乙烯共聚物石墨烯复合气凝胶(即本发明中的复合气凝胶)。
实施例2
按照实施例1中方法制备马来酰亚胺石墨烯复合气凝胶，将0.2g马来酰亚胺石墨烯复合气凝胶放入装有20g切片石蜡的聚四氟乙烯烧杯中，将容器置于真空烘箱中保持100℃2h后，熔融的石蜡渗透进入所述的马来酰亚胺石墨烯复合气凝胶中，从而得到气凝胶相变复合材料；将气凝胶相变复合材料从容器中取出，随后擦干气凝胶相变复合材料表面的过量的相变材料，室温放置2小时后，称重后得到马来酰亚胺基共聚物石墨烯气凝胶相变复合材料(吸附石蜡约10g)。
实施例3
将实施例2中的相变材料由石蜡替换成十八醇(购自阿拉丁)，其余实验与实施例2一致。
所得相变复合材料回收效果与实施例2接近。
实施例4
将实施例2中所得相变复合材料样品研磨成粉末，取5g粉末，置于带盖玻 璃瓶中，然后加入0.2g质量分数为25％的氨水和30ml水，加热至95℃并在1000r/min的磁力搅拌条件下维持1h，之后趁热过滤(图4中的a)，滤液加热浓缩至约5ml后，放入模具冰箱预冷冻后，置入冷冻干燥机冷冻干燥(温度为-30℃以下，压力为10Pa以下)得到回收的聚合物气凝胶(图4中的c)，滤饼自然晾干后放入小烧杯，加热100熔融后保持1h，降温后得到高附加值产品石墨烯相变复合材料，根据需要切割成型(图4中的b)。可见，本发明中的具有光热转化功能的可回收储热相变复合材料中的材料可以分别回收重复利用。
实施例5
取91.5g水，将其加入到带盖玻璃瓶中，再加入3.5g质量分数为25％的氨水和5g马来酸酐-苯乙烯共聚物，将玻璃瓶盖旋紧后放入烘箱中保持95℃，4小时后取出得到均一的5％质量分数聚合物溶液。
将聚合物溶液倒入6个模具中，每个模具倒入15ml溶液，并置于-30℃冰箱冷冻2小时，将冷冻好的样品转移到冷冻干燥机中冷冻干燥(-30℃以下，10Pa以下)72小时后，取出得到的水溶性聚合物气凝胶；将水溶性聚合物气凝胶置入恒温容器中180℃进行热处理，以脱水脱氨得到马来酰亚胺基气凝胶。
将0.5g马来酰亚胺基聚合物气凝胶放入装有20g切片石蜡的30ml聚四氟乙烯烧杯中，将容器置于真空烘箱中保持100℃2h后，得到气凝胶相变复合材料；将气凝胶相变复合材料从容器中取出，随后擦干气凝胶相变复合材料表面的过量的相变材料，室温放置2小时后，称重得到马来酰亚胺基共聚物气凝胶相变复合材料(吸附石蜡约7g)。
实施例6
将实施例1中的微波处理时间改为1s，其他制备步骤与实施例1相同。
实施例7
取93.2g水，将其加入到带盖玻璃瓶中，再加入2.8g质量分数为25％的氨水和4g马来酸酐-苯乙烯共聚物，将玻璃瓶盖旋紧后放入烘箱中保持95℃，四小时后取出得到均一的4％质量分数聚合物溶液。
向玻璃瓶内加入100g 20mg/ml氧化石墨烯水溶液，再加入4g抗坏血酸，1000r/min下磁力搅拌5min，待混合均匀后，迅速将其倒入下底面为铜，壁为聚四氟乙烯的圆柱模具中，并将其放置于液氮浴中的铜柱上。待预冻完成后，放入冷冻干燥机中，(-30℃以下，10Pa以下)冷冻干燥72小时后，得到各向异性的水溶性GO/SMI复合气凝胶。
然后将该气凝胶置于充有氮气的聚四氟乙烯内胆中，放入180℃恒温箱中热处理2h，取出样品放入充有氮气的密闭石英罐中，微波处理(辐照功率为800W)5s得到马来酰亚胺苯乙烯共聚物石墨烯复合气凝胶。
实施例8
取93.2g水，将其加入到带盖玻璃瓶中，再加入2.8g质量分数为25％的氨水和4g马来酸酐-苯乙烯共聚物，将玻璃瓶盖旋紧后放入烘箱中保持95℃，四小时后取出得到均一的4％质量分数聚合物溶液。
向玻璃瓶内加入100g 20mg/ml氧化石墨烯水溶液，再加入4g抗坏血酸，1000r/min下磁力搅拌5min，待混合均匀后，迅速将其倒入下底面为铜，壁为聚四氟乙烯的圆柱模具中，并将其放置于液氮浴中的铜柱上。待预冻完成后，放入冷冻干燥机中，(-30℃以下，10Pa以下)冷冻干燥72小时后，得到各向异性的水溶性GO/SMI复合气凝胶。
然后将该气凝胶置于充有氮气的聚四氟乙烯内胆中，放入180℃恒温箱中热处理2h，取出样品放入充有氮气的密闭石英罐中，微波处理(辐照功率为800W)7s得到马来酰亚胺苯乙烯共聚物石墨烯复合气凝胶。
实施例9
取内胆为聚四氟乙烯的反应釜，加入20.5g水，再加入4g质量分数为25％的氨水和0.5g马来酸酐-苯乙烯共聚物，将反应釜后放入烘箱中保持150℃，10小时后取出得到均一的聚合物溶液。
向反应釜中内加入75g 40mg/ml氧化石墨烯水溶液，再加入3g抗坏血酸，1000r/min下磁力搅拌5min，待混合均匀后，迅速将其倒入下底面为铜，壁为聚四氟乙烯的圆柱模具中，并将其放置于液氮浴中的铜柱上。待预冻完成后，放入冷冻干燥机中，(-30℃以下，10Pa以下)冷冻干燥72小时后，得到各向异性的水溶性GO/SMI复合气凝胶。
然后将该气凝胶置于充有氮气的聚四氟乙烯内胆中，放入200℃恒温箱中热处理2h，取出样品放入充有氮气的密闭石英罐中，微波处理(辐照功率为500W)3s得到马来酰亚胺苯乙烯共聚物石墨烯复合气凝胶。
将0.2g马来酰亚胺基聚合物气凝胶放入装有20g切片石蜡的30ml聚四氟乙烯烧杯中，将容器置于真空烘箱中保持100℃2h后，得到气凝胶相变复合材料；将气凝胶相变复合材料从容器中取出，随后擦干气凝胶相变复合材料表面的过量的相变材料，室温放置2小时后，得到共聚物石墨烯气凝胶相变复合材料(吸附石蜡约4g)。
实施例10
在带盖玻璃瓶中加入91.5g水，再加入3.5g质量分数为25％的氨水和5g马来酸酐-苯乙烯共聚物，将玻璃瓶盖旋紧后放入烘箱中保持95℃，4小时后取出得到均一的5％质量分数聚合物溶液，室温下晾干得含有马来酰胺酸、马来酸铵基团的聚合物。
将所得聚合物放入在带盖玻璃瓶中，加入到41.5g水，再加入0.04g质量分数为25％的氨水，将玻璃瓶盖旋紧后放入烘箱中保持20℃，0.5小时后取出得到均一的聚合物溶液。
向玻璃瓶中内加入50g 6mg/ml氧化石墨烯水溶液，再加入0.9g抗坏血酸， 1000r/min下磁力搅拌5min，待混合均匀后，迅速将其倒入下底面为铜，壁为聚四氟乙烯的圆柱模具中，并将其放置于液氮浴中的铜柱上。待预冻完成后，放入冷冻干燥机中，(-30℃以下，10Pa以下)冷冻干燥72小时后，得到各向异性的水溶性GO/SMI复合气凝胶。
然后将该气凝胶置于充有氮气的聚四氟乙烯内胆中，放入130℃恒温箱中热处理2h，取出样品放入充有氮气的密闭石英罐中，微波处理(辐照功率为2000W)3s得到马来酰亚胺苯乙烯共聚物石墨烯复合气凝胶。
将0.2g马来酰亚胺基聚合物气凝胶放入装有20g切片石蜡的30ml聚四氟乙烯烧杯中，将容器置于真空烘箱中保持100℃2h后，得到气凝胶相变复合材料；将气凝胶相变复合材料从容器中取出，随后擦干气凝胶相变复合材料表面的过量的相变材料，室温放置2小时后，得到共聚物石墨烯气凝胶相变复合材料(约吸附石蜡6g)。
相变温度和相变潜热与实施例2接近。
比较例1
取91.5g水，将其加入到带盖玻璃瓶中，再加入3.5g 25％氨水和5g马来酸酐-苯乙烯共聚物，将玻璃瓶盖旋紧后放入烘箱中保持95℃，四小时后取出得到均一的5％质量分数聚合物溶液。
将聚合物溶液倒入6个模具中，每个模具倒入15ml溶液，并置于-30℃冰箱冷冻2小时，将冷冻好的样品转移到冷冻干燥机中(温度为-30℃以下，压力为10Pa以下)冷冻干燥72小时后，取出得到的水溶性聚合物气凝胶；将水溶性聚合物气凝胶置入恒温容器中180℃进行热处理2h，以脱水脱氨得到马来酰亚胺基气凝胶。
比较例2
将20g切片石蜡的30ml聚四氟乙烯烧杯中，将容器置于真空烘箱中保持 100℃2h后，取出，室温放置2小时后，得到石蜡相变材料(即纯的相变材料)。
测试例
实施例1及实施例6-8所制备气凝胶ID/IG测试结果列于表1，实施例2、比较例2和实施例5所制备的相变材料的泄漏情况列于表2；比较例1和实施例4的DSC曲线和玻璃化转变温度Tg示于图1；比较例1和实施例4的热失重曲线列于图2；实施例2和实施例5的相变材料在一个太阳光照强度和移除光照温度曲线列于图3。
图3的测试结果表明，石墨烯赋予了相变材料光热转化功能，含有石墨烯的气凝胶相变复合材料可以在30min内升温至70℃以上，并可长时间保持温度在50℃以上，具有良好的光热转化性能，可以实现对太阳能的高效利用。按照同样的方法对实施例6中的复合相变材料进行了测试，实施例6与实施例2相比，实施例2中的复合相变材料的光热转化性能优于实施例6。
表1
表1的测试结果表明，本发明所制备的复合气凝胶还原效率很高，3s即可达到较高的还原程度，有利于快速大量工业制备。
表2

表2的测试结果表明，气凝胶对相变材料的防泄漏效果较好，具有较好的使用前景。
表3
根据表3数据可知，多孔气凝胶对相变材料造成的潜热造成的损失很小，使用不同的有机相变材料均可制备高潜热值的相变复合材料，气凝胶的加入会略微降低相变材料的熔融温度和凝固温度。
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都通过引 用并入本文。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本申请文件中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。在下文中，各个技术方案之间原则上可以相互组合而得到新的技术方案，这也应被视为在本文中具体公开。
在本说明书的上下文中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。
而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此而形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合是明显不合理的。

Claims (16)

  1. 一种复合气凝胶，含有聚合物和石墨烯，所述聚合物中含有含马来酸酐基团的结构单元和含马来酰亚胺基团的结构单元，其中所述马来酸酐基团指的是所述马来酰亚胺基团指的是
  2. 根据权利要求1所述的复合气凝胶，其特征在于：
    所述复合气凝胶表面的拉曼光谱ID/IG平均值小于等于1.2，优选小于等于0.9，更优选小于等于0.85；和/或，
    石墨烯与聚合物的质量比为(1：20)-(10：1)，优选为(1：10)-(6:1)，更优选(1：5)-(1：1)。
  3. 根据权利要求1所述的复合气凝胶，其特征在于：
    所述复合气凝胶中的聚合物能够溶于0-150℃的氨水中，形成聚合物水溶液；和/或，
    所述石墨烯通过将氧化石墨烯还原后得到，优选将氧化石墨烯先用还原剂进行预还原，再进行微波还原后得到；更优选地，
    所述还原剂选自抗坏血酸、没食子酸、硼氢化钠、氨基酸中的至少一种。
  4. 根据权利要求1所述的复合气凝胶，其特征在于：
    以含马来酸酐基团的结构单元和含马来酰亚胺基团的结构单元的总摩尔量为100％计，所述聚合物中含马来酰亚胺基团的结构单元的摩尔比例为5％-70％，优选为10％-60％；更优选为20％-50％。
  5. 根据权利要求1所述的复合气凝胶，其特征在于：
    所述聚合物衍生自含有含马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐基团的结构单元中的一种或几种的聚合物原料；优选地，所述聚合物原料是包括马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐中的一种或几种的聚合单体与烯烃单体的共聚物；更优选地，所述烯烃单体为α-甲基苯乙烯、苯乙烯、异丁烯中的至少一种。
  6. 根据权利要求1-5之一所述的复合气凝胶，其特征在于：
    所述复合气凝胶通过将含有含马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐基团的结构单元中的一种或几种的聚合物原料与氨水在密闭情况下发生反应，再与氧化石墨烯、还原剂混合后，经预冷冻、冷冻干燥、脱水脱氨、还原处理后制备得到。
  7. 一种权利要求1-6之一所述的复合气凝胶的制备方法，包括将含有含马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐基团的结构单元中的一种或几种的聚合物原料与氨水在密闭情况下发生反应，再与氧化石墨烯、还原剂混合后，经预冷冻、冷冻干燥、脱水脱氨、还原处理，得到所述复合气凝胶。
  8. 根据权利要求7所述的制备方法，其特征在于包括以下步骤：
    (1)将所述聚合物原料与氨水在密闭情况下发生反应，得到聚合物水溶液；
    (2)将步骤(1)得到的聚合物水溶液与氧化石墨烯、还原剂混合得到混合液，之后进行预冷冻，再经冷冻干燥，得到复合聚合物；
    (3)将步骤(2)得到的复合聚合物进行热处理，之后进行微波辐照，得到所述复合气凝胶。
  9. 根据权利要求8所述的制备方法，其特征在于：
    步骤(1)中：
    以反应体系的总质量为100％计，聚合物原料用量的质量分数为0.1％-30％，优选为0.5％-10％，更优选为1％-5％，以氨水中氨的质量计，氨用量的质量分数为0.001％-30％，优选为0.01％-10％，更优选为0.1％-1％，其余组分为水；和/或，
    反应的条件包括：
    反应温度为0-200℃，优选为50-150℃，更优选为80-100℃，和/或，反应时间为0.01-100h，优选为0.5-10h，更优选为1-5h。
  10. 根据权利要求8所述的制备方法，其特征在于：
    步骤(2)中：
    所述氧化石墨烯来源于含有氧化石墨烯的分散液，分散液中氧化石墨烯的浓度为1-100mg/mL，优选为3-30mg/mL，更优选5-20mg/mL；和/或，
    所述还原剂选自抗坏血酸、没食子酸、硼氢化钠、氨基酸中的至少一种；和/或，
    所述还原剂与氧化石墨烯的质量比为1：(0.1-20)，优选为1:(1-3)；和/或，
    所述预冷冻时混合液的各个方向冷源温度相同或不同，优选地，所述预冷冻时混合液的各个方向冷源温度不同；更优选地，所述预冷冻时混合液所处的单向冷源温度不同；和/或，
    冷冻干燥的条件包括：温度为(-10)℃以下；和/或，真空度为1000Pa以下。
  11. 根据权利要求8所述的制备方法，其特征在于：
    步骤(3)中：
    热处理的条件包括：温度为100-300℃，优选为120-220℃，更优选为160- 200℃；热处理时间为0.1-10小时，优选为0.5-3小时，更优选为1-2小时；和/或，
    微波辐照功率为500-2000W；微波辐照时间为1-10s，优选为2-7s，更优选为3-5s。
  12. 根据权利要求7-11之一所述的制备方法，其特征在于：
    所述聚合物原料能够与氨水反应得到水溶性聚合物；和/或，
    所述聚合物原料是包括马来酸酐、马来酰亚胺、马来酸及铵盐、马来酰胺酸及铵盐中的一种或几种的聚合单体与烯烃单体的共聚物；更优选地，所述烯烃单体包括α-甲基苯乙烯、苯乙烯、异丁烯中的至少一种；
    优选地，所述聚合物原料为苯乙烯马来酸酐共聚物、马来酸酐异丁烯共聚物中的至少一种。
  13. 一种可回收储热相变复合材料，含有复合气凝胶和负载于所述复合气凝胶中的相变材料；
    所述复合气凝胶为权利要求1-6之一所述的复合气凝胶或者权利要求7-12之一所述的制备方法制备得到的复合气凝胶。
  14. 根据权利要求13所述的可回收储热相变复合材料，其特征在于：
    所述复合气凝胶与所述相变材料的质量比为1：(0.05-50)；和/或，
    所述相变材料为有机相变材料，优选为水溶性相变材料和/或非水溶性相变材料，更优选为聚乙二醇、月桂酸、十八醇、石蜡中的至少一种；和/或，
    在所述相变材料为液态的温度条件下，可回收储热相变复合材料中相变材料的泄漏量小于10wt％，优选小于5wt％，更优选小于2wt％。
  15. 权利要求13或14所述的可回收储热相变复合材料的制备方法，包括将所述相变材料负载在所述复合气凝胶中；
    优选地，可回收储热相变复合材料的制备方法包括：采用权利要求7-12之一所述的制备方法，得到的复合气凝胶；再将所述相变材料负载在所述复合气凝胶中。
  16. 权利要求13或14所述的可回收储热相变复合材料在建筑节能、空调系统、废热利用、太阳能储存领域中的应用。
PCT/CN2023/117746 2022-09-09 2023-09-08 复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用 WO2024051826A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211101221.9A CN117720767A (zh) 2022-09-09 2022-09-09 复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用
CN202211101221.9 2022-09-09

Publications (1)

Publication Number Publication Date
WO2024051826A1 true WO2024051826A1 (zh) 2024-03-14

Family

ID=90192088

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/117746 WO2024051826A1 (zh) 2022-09-09 2023-09-08 复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用

Country Status (2)

Country Link
CN (1) CN117720767A (zh)
WO (1) WO2024051826A1 (zh)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150259212A1 (en) * 2012-08-23 2015-09-17 Monash University Graphene-based materials
CN106422995A (zh) * 2015-08-11 2017-02-22 中国科学院化学研究所 一种石墨烯气凝胶和其杂化复合材料及其制备方法与应用
US20180145328A1 (en) * 2015-08-07 2018-05-24 Board Of Regents, The University Of Texas System Graphene oxide-polymer aerogels and electrodes
CN109385254A (zh) * 2018-11-26 2019-02-26 同济大学 一种石墨烯弹性聚合物相变复合材料及其制备方法
CN110591142A (zh) * 2019-09-23 2019-12-20 陕西科技大学 一种石墨烯/聚酰亚胺复合气凝胶的制备方法
CN110804420A (zh) * 2019-10-09 2020-02-18 北京化工大学 一种基于高导热各向异性石墨烯骨架的相变复合材料及其制备方法
CN110818945A (zh) * 2019-12-03 2020-02-21 四川大学 一种有序孔结构聚酰亚胺/石墨烯复合气凝胶及其制备方法和用途
CN112852386A (zh) * 2021-01-25 2021-05-28 武汉科技大学 一种高取向层状石墨烯气凝胶相变复合材料及其制备方法
CN113527825A (zh) * 2020-04-13 2021-10-22 中国科学院大连化学物理研究所 一种石墨烯基柔性复合定型相变材料膜及制备和应用
CN113698915A (zh) * 2020-05-22 2021-11-26 中国科学院大连化学物理研究所 一种石墨烯基多重响应的定型复合相变材料及制备和应用

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150259212A1 (en) * 2012-08-23 2015-09-17 Monash University Graphene-based materials
US20180145328A1 (en) * 2015-08-07 2018-05-24 Board Of Regents, The University Of Texas System Graphene oxide-polymer aerogels and electrodes
CN106422995A (zh) * 2015-08-11 2017-02-22 中国科学院化学研究所 一种石墨烯气凝胶和其杂化复合材料及其制备方法与应用
CN109385254A (zh) * 2018-11-26 2019-02-26 同济大学 一种石墨烯弹性聚合物相变复合材料及其制备方法
CN110591142A (zh) * 2019-09-23 2019-12-20 陕西科技大学 一种石墨烯/聚酰亚胺复合气凝胶的制备方法
CN110804420A (zh) * 2019-10-09 2020-02-18 北京化工大学 一种基于高导热各向异性石墨烯骨架的相变复合材料及其制备方法
CN110818945A (zh) * 2019-12-03 2020-02-21 四川大学 一种有序孔结构聚酰亚胺/石墨烯复合气凝胶及其制备方法和用途
CN113527825A (zh) * 2020-04-13 2021-10-22 中国科学院大连化学物理研究所 一种石墨烯基柔性复合定型相变材料膜及制备和应用
CN113698915A (zh) * 2020-05-22 2021-11-26 中国科学院大连化学物理研究所 一种石墨烯基多重响应的定型复合相变材料及制备和应用
CN112852386A (zh) * 2021-01-25 2021-05-28 武汉科技大学 一种高取向层状石墨烯气凝胶相变复合材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YAO, YUAN ET AL.: "Preparation and application of recyclable polymer aerogels from styrene-maleic anhydride alternating copolymers", CHEMICAL ENGINEERING JOURNAL, vol. 455, 14 November 2022 (2022-11-14), XP087259101, DOI: 10.1016/j.cej.2022.140363 *

Also Published As

Publication number Publication date
CN117720767A (zh) 2024-03-19

Similar Documents

Publication Publication Date Title
WO2020253094A1 (zh) 一种氮化硼纳米管气凝胶/相变导热复合材料及其制备方法
GB2501393A (en) A composite phase change material
CN104559936B (zh) 一种中温用相变蓄热材料及其制备方法
CN110205100B (zh) 氧化石墨烯/膨胀石墨气凝胶相变复合材料及其制备方法
CN110016323B (zh) 一种自修复凝胶基相变材料及其制备方法
CN106118610B (zh) 聚乙二醇/石墨烯定型相变材料的制备方法
CN110791256A (zh) 一种生物质复合蓄热材料及其制备方法
CN106967390A (zh) 一种低温无机复合相变储热材料及其制备方法
CN109847723A (zh) 一种聚乙烯醇/zif-8多孔复合材料的制备方法
CN105754554A (zh) 一种含纳米TiO2的纤维素基低温相变储能微胶囊及其制备方法
WO2024051826A1 (zh) 复合气凝胶、具有光热转化功能的可回收储热相变复合材料及制法和应用
CN110373161A (zh) 一种定型相变储能复合材料及其制备方法
CN101838521B (zh) 二元脂肪酸/皂土复合相变储能材料的制备方法
Ma et al. Preparation and properties of composite shape-stabilized phase change material for asphalt mixture
CN116948606A (zh) 一种基于火龙果皮衍生多孔碳储热复合相变材料及其制备方法和应用
CN116855096A (zh) 一种共晶相变复合保温板及其制备方法和应用
CN109705813A (zh) 一种蓄热恒温纳米复合相变材料及其制备方法
CN110105925B (zh) 十六胺/二氧化硅复合定形相变材料的制备方法
CN110041891B (zh) 聚乙二醇/二氧化硅定形相变材料的制备方法
CN114479770A (zh) 一种光热相变储能材料及其制备方法和应用
CN104592945A (zh) 一种阻燃型有机相变材料及其制备方法
CN102604598B (zh) 微尺度聚氯乙烯包覆十水硫酸钠相变储能材料及其制备方法
CN110157387A (zh) 高吸光、高导热的脂肪酸/纳米复合物改性蛭石复合相变储能材料及其制备方法
CN112063370A (zh) 一种导热增强的自修复复合相变材料及其制备方法与应用
WO2024051811A1 (zh) 可回收聚合物气凝胶、蓄冷相变复合材料及制法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23862520

Country of ref document: EP

Kind code of ref document: A1