CN110408167B - Aerogel, preparation method and application thereof, high-temperature heat-insulating material or light-weight heat-preventing/insulating material - Google Patents
Aerogel, preparation method and application thereof, high-temperature heat-insulating material or light-weight heat-preventing/insulating material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011810 insulating material Substances 0.000 title description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000012774 insulation material Substances 0.000 claims abstract description 21
- 238000009413 insulation Methods 0.000 claims abstract description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 118
- 229920001568 phenolic resin Polymers 0.000 claims description 117
- 239000005011 phenolic resin Substances 0.000 claims description 117
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 47
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 41
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- 229920000877 Melamine resin Polymers 0.000 claims description 25
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 20
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 18
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- 239000004640 Melamine resin Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 230000002265 prevention Effects 0.000 abstract description 11
- 238000002679 ablation Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 238000009991 scouring Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 81
- 238000003756 stirring Methods 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000005303 weighing Methods 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011240 wet gel Substances 0.000 description 12
- 238000001879 gelation Methods 0.000 description 10
- 239000000499 gel Substances 0.000 description 8
- -1 phenol aldehyde Chemical class 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- 230000002787 reinforcement Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
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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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of heat insulation materials, and particularly provides aerogel, a preparation method and application thereof, a high-temperature heat insulation material or a light-weight heat prevention/insulation material. The aerogel comprises a phenolic aldehyde skeleton and a zirconium dioxide skeleton, wherein the zirconium dioxide skeleton is uniformly distributed in the phenolic aldehyde skeleton, and the phenolic aldehyde skeleton and the zirconium dioxide skeleton form a molecular network structure. The aerogel has the advantages of low density, high strength, excellent high-temperature scouring resistance and oxidation resistance, and ablation and heat insulation integrated functions.
Description
Technical Field
The invention relates to the field of heat insulation materials, in particular to aerogel, a preparation method and application thereof, a high-temperature heat insulation material or a light-weight heat prevention/insulation material.
Background
At present, with the development of hypersonic aircrafts towards high mach number and high endurance, the pneumatic heating environment faced by the aircrafts is worse, so that higher requirements are also put forward on the thermal protection materials of reentry aircrafts, the thermal protection structure of the hypersonic aircrafts is required to be simple, convenient and light, and the hypersonic aircrafts are required to be multifunctional, namely, the hypersonic aircrafts have high-efficiency heat insulation capability while realizing heat prevention. In the nineties of the last century, the NASA Ames research center in the united states uses Phenolic resin as a matrix and Carbon fiber as a reinforcement, and develops a low-density ablative material with a porous structure, namely a Phenolic Impregnated Carbon ablative material (PICA) by a polymer phase separation principle, and the low-density ablative material is successfully applied to large-area thermal protection structures of a star-dust returnable capsule and a hunting seat plan, so that the application of the porous material in the space exploration field is opened.
Aerogel, as a three-dimensional network structure formed by crosslinking nanoparticles, has received increasing attention due to its advantages of ultra-low density, high porosity, low thermal/electrical conductivity, and the like. The appearance of aerogel materials, particularly the development of organic aerogel materials, can meet the requirements of aerospace vehicles on heat-proof and heat-insulating materials in various temperature intervals. Organic aerogel has become the first choice material in the aerospace field as one of the most promising novel high-efficiency heat-proof materials. However, the skeleton structure of the organic aerogel mainly consists of polymer organic chains, and the polymer chains are easily cracked into small molecular substances in a high-temperature aerobic environment, so that the oxidation resistance and the high-temperature scouring resistance of the heat-proof material prepared by taking the organic aerogel as a matrix are greatly limited.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide aerogel, which has low density, high strength, excellent high-temperature scouring resistance and oxidation resistance, and ablation and heat insulation integration functions.
The second purpose of the invention is to provide a preparation method of the aerogel, the method is scientific and reasonable, the process is simple, and the prepared aerogel has the advantages of low density, high strength, excellent high-temperature scouring resistance and excellent oxidation resistance.
The third purpose of the invention is to provide the application of the aerogel in high-temperature heat-insulating materials or light-weight heat-preventing/insulating materials.
A fourth object of the present invention is to provide a high temperature insulation material or a lightweight heat prevention/insulation material.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides an aerogel, which comprises a phenolic aldehyde skeleton and a zirconium dioxide skeleton, wherein the zirconium dioxide skeleton is uniformly distributed in the phenolic aldehyde skeleton, and the phenolic aldehyde skeleton and the zirconium dioxide skeleton form a molecular network structure.
As a further preferred embodiment, the mass ratio of zirconium dioxide to phenol aldehyde is 1:10 to 1:2, preferably 1:8 to 1: 4.
As a further preferred technical scheme, the density of the aerogel is 0.05-0.6g/cm3；
Preferably, the aerogelThe adhesive has a thermal conductivity at room temperature of 0.03-0.07W (m.K)-1；
Preferably, the aerogel has a compressive strength of 0.5 to 50 MPa.
In a second aspect, the present invention provides a method for preparing the aerogel, comprising the following steps: mixing phenolic resin, a zirconium source, a curing agent and a solvent, and then sequentially carrying out sol-gel reaction, aging and drying to obtain the aerogel.
As a further preferred technical solution, the method comprises the steps of:
(a) preparing zirconium dioxide sol: mixing a zirconium source and a solvent;
(b) preparing a phenolic resin solution: mixing phenolic resin and a solvent;
(c) uniformly mixing the zirconium dioxide sol in the step (a), the phenolic resin solution in the step (b) and a curing agent until a clear transparent solution is obtained;
(d) and (c) carrying out sol-gel reaction on the clear transparent solution obtained in the step (c) under the conditions of sealing and 60-180 ℃, and then aging and drying to obtain the aerogel.
As a further preferred embodiment, in step (a), the zirconium source comprises at least one of zirconium acetate, zirconium oxychloride, or zirconium isopropoxide;
preferably, in step (a), the zirconium source is 5-20% by mass of the zirconia sol;
preferably, in step (b), the weight average molecular weight of the phenolic resin is 500-2000;
preferably, in the step (b), the mass percentage of the phenolic resin in the phenolic resin solution is 5-60%;
preferably, in step (a) and/or (b), the solvent comprises an alcohol, preferably comprising an alcohol of C1-C4, further preferably comprising at least one of methanol, ethanol or isopropanol.
As a further preferable technical scheme, in the step (c), the mass ratio of the zirconium source in the zirconium dioxide sol to the phenolic resin in the phenolic resin solution is 1:20-1: 5;
preferably, in step (c), the curing agent comprises at least one of hexamethylenetetramine, aniline, melamine or melamine resin;
preferably, in the step (c), the mass ratio of the phenolic resin to the curing agent is 3:1-10: 1.
As a further preferred technical solution, in the step (d), the aging time is 2 to 7 days;
preferably, in step (d), the drying comprises atmospheric drying; preferably, the drying under normal pressure comprises drying at 20-30 deg.C for 1-3 days first, and then at 50-80 deg.C for 1-2 days.
In a third aspect, the invention provides an application of the aerogel or the aerogel prepared by the method in high-temperature heat insulation materials or light-weight heat prevention/insulation materials.
In a fourth aspect, the present invention provides a high temperature insulation material or a lightweight insulation material, comprising the aerogel or the aerogel prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the aerogel provided by the invention takes a phenolic aldehyde skeleton as an organic main phase and a zirconium dioxide skeleton as an inorganic hybrid phase, and a molecular network structure can ensure the uniformity and consistency of all components of the aerogel; the aerogel integrates the advantages of low density and excellent heat-insulating property of phenolic aldehyde aerogel and ablation resistance and ceramic property of zirconium dioxide aerogel, can overcome the problem of cracking of the existing phenolic aldehyde organic aerogel in a high-temperature aerobic environment, has low density, high strength, excellent high-temperature scouring resistance and oxidation resistance, has the function of ablation heat-insulating integration, and has wide application prospect in the fields of high-temperature heat insulation, light weight heat prevention/insulation and the like.
The preparation method of the aerogel provided by the invention is scientific and reasonable, the process is simple, and the prepared aerogel has the advantages of low density, high strength, and excellent high-temperature scouring resistance and oxidation resistance.
Drawings
FIG. 1 is an infrared spectrum of aerogel in comparative example 1 and example 3;
FIG. 2 is a scanning electron micrograph of the aerogel in comparative example 1 and examples 3 to 5;
FIG. 3 is a thermogravimetric plot of the aerogels in comparative example 1 and examples 3-5.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
It should be noted that:
in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0.5 to 50" means that all real numbers between "0.5 to 50" have been listed herein, and "0.5 to 50" is only a shorthand representation of the combination of these numbers.
In the present invention, unless otherwise specified, the individual operation steps may be performed sequentially or may not be performed in sequence. Preferably, the steps of the operations herein are performed sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
According to one aspect of the present invention, there is provided in at least one embodiment an aerogel comprising a phenolic skeleton and a zirconium dioxide skeleton, the zirconium dioxide skeleton being uniformly distributed in the phenolic skeleton and forming a molecular network structure.
The aerogel takes a phenolic aldehyde skeleton as an organic main phase and a zirconium dioxide skeleton as an inorganic hybrid phase, and the uniformity and consistency of all components of the aerogel can be ensured by a molecular network structure; the aerogel integrates the advantages of low density and good heat-insulating property of phenolic aerogel, ablation resistance and ceramic property of zirconium dioxide aerogel (zirconium dioxide can also react with carbon in phenolic aldehyde to generate ZrC at high temperature), can overcome the problem of cracking of the existing phenolic organic aerogel at high temperature in an aerobic environment, has low density, high strength, excellent high-temperature scouring resistance and oxidation resistance, has the function of integration of ablation and heat insulation, and has wide application prospect in the fields of high-temperature heat insulation, light prevention/heat insulation and the like.
It should be noted that:
the 'phenolic skeleton' refers to a three-dimensional nano porous structure formed by crosslinking and winding phenolic particles.
The zirconium dioxide skeleton refers to a three-dimensional nano porous structure formed by cross-linking and winding zirconium dioxide particles.
The "molecular network structure" refers to the mixing of the phenolic skeleton and the zirconium dioxide skeleton on a molecular scale, which is achieved by the force between the molecules.
In a preferred embodiment, the mass ratio of zirconium dioxide to phenol aldehyde is from 1:10 to 1:2, preferably from 1:8 to 1: 4. The above mass ratio is typically, but not limited to, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3 or 1: 2. When the mass ratio of zirconium dioxide to phenolic aldehyde is within the above range, the structure of the aerogel is more uniform and stable, and the comprehensive performance is more excellent.
In a preferred embodiment, the aerogel has a density of 0.05 to 0.6g/cm3. The density is typically, but not limited to, 0.05g/cm3、0.1g/cm3、0.15g/cm3、0.2g/cm3、0.25g/cm3、0.3g/cm3、0.35g/cm3、0.4g/cm3、0.45g/cm3、0.5g/cm3、0.55g/cm3Or 0.6g/cm3。
Preferably, the aerogel has a room temperature thermal conductivity of 0.03-0.07W (m.K)-1. The room temperatureThe thermal conductivity is the thermal conductivity at 25 ℃. The above-mentioned thermal conductivity at room temperature is typically, but not limited to, 0.03W (m.K)-1、0.04W·(m·K)-1、0.05W·(m·K)-1、0.06W·(m·K)-1Or 0.07W (m.K)-1。
Preferably, the aerogel has a compressive strength of 0.5 to 50 MPa. The above compressive strength is typically, but not limited to, 0.5MPa, 1MPa, 4MPa, 6MPa, 8MPa, 10MPa, 15MPa, 20MPa, 25MPa, 30MPa, 35MPa, 40MPa, 45MPa or 50 MPa.
According to another aspect of the present invention, there is provided in at least one embodiment a method of preparing the aerogel described above, comprising the steps of: mixing phenolic resin, a zirconium source, a curing agent and a solvent, and then sequentially carrying out sol-gel reaction, aging and drying to obtain the aerogel. The method is scientific and reasonable, the process is simple, and the prepared aerogel has the advantages of low density, high strength, excellent high-temperature scouring resistance and excellent oxidation resistance.
In a preferred embodiment, the method comprises the steps of:
(a) preparing zirconium dioxide sol: mixing a zirconium source and a solvent;
(b) preparing a phenolic resin solution: mixing phenolic resin and a solvent;
(c) uniformly mixing the zirconium dioxide sol in the step (a), the phenolic resin solution in the step (b) and a curing agent until a clear transparent solution is obtained;
(d) and (c) carrying out sol-gel reaction on the clear transparent solution obtained in the step (c) under the conditions of sealing and 60-180 ℃, and then aging and drying to obtain the aerogel.
The above-mentioned "clear transparent solution" means a solution containing no insoluble matter. The above temperature is typically, but not limited to, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃. The preparation method in the preferred embodiment has the advantages of simple process, mild and rapid conditions, low equipment requirement and low preparation cost, is suitable for industrial production, and the obtained aerogel is easy for post processing and forming and post size cutting, has excellent performance and is easy for industrial application.
In a preferred embodiment, in step (a), the zirconium source comprises at least one of zirconium acetate, zirconium oxychloride, or zirconium isopropoxide. Typical, but non-limiting, such sources of zirconium are zirconium acetate, zirconium oxychloride, zirconium isopropoxide, a combination of zirconium acetate and zirconium oxychloride, a combination of zirconium oxychloride and zirconium isopropoxide, a combination of zirconium acetate and zirconium isopropoxide, or a combination of zirconium acetate, zirconium oxychloride and zirconium isopropoxide, and the like.
Preferably, in step (a), the solvent comprises an alcohol, preferably comprising an alcohol of C1-C4, further preferably comprising at least one of methanol, ethanol or isopropanol. The C1-C4 alcohol is a monohydric or polyhydric alcohol having 1, 2, 3 or 4 carbon atoms. Typical but non-limiting examples of such C1-C4 alcohols are methanol, ethanol, isopropanol, a combination of methanol and ethanol, a combination of ethanol and isopropanol, a combination of methanol and isopropanol, or a combination of methanol, ethanol and isopropanol, and the like.
Preferably, in step (a), the zirconium source is present in the zirconia sol in an amount of 5% to 20% by weight, preferably 5% to 15% by weight. Such amounts are typically, but not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.
In a preferred embodiment, in step (b), the weight average molecular weight of the phenolic resin is 500-2000, preferably 700-1500. The above weight average molecular weight is typically, but not limited to, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, or 2000.
Preferably, in step (b), the solvent comprises an alcohol, preferably comprising an alcohol of C1-C4, further preferably comprising at least one of methanol, ethanol or isopropanol. The C1-C4 alcohol is a monohydric or polyhydric alcohol having 1, 2, 3 or 4 carbon atoms. Typical but non-limiting examples of such C1-C4 alcohols are methanol, ethanol, isopropanol, a combination of methanol and ethanol, a combination of ethanol and isopropanol, a combination of methanol and isopropanol, or a combination of methanol, ethanol and isopropanol, and the like.
Preferably, in the step (b), the mass percentage of the phenolic resin in the phenolic resin solution is 5-60%, preferably 10-50%. Such amounts are typically, but not limited to, 5%, 10%, 15%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 45%, 50%, 55%, or 60%.
Alternatively, the phenolic resin is prepared by the following method: mixing phenol and formaldehyde solution, mixing with catalyst (hydrochloric acid or alkali) to obtain mixed solution, heating the mixed solution in water bath, wherein when the mixed solution begins to boil, the reaction is in progress (the reaction is exothermic), and when the boiling is stopped, the reaction is completed. And after the boiling is stopped, heating is continued for about 10 minutes so as to be beneficial to fully layering the phenolic resin and the aqueous solution, wherein the upper layer is water, and the lower layer is the phenolic resin. In the above method, if phenol is used in excess and an acid is used as a catalyst, the product is a linear polymer resin; if the formaldehyde solution is excessive and ammonia water is used as the catalyst, the product is a three-dimensional polymer resin.
It should be understood that the above is only one method for preparing the phenolic resin, and the phenolic resin can be prepared by other methods in the prior art, or by the prior art, and the invention is not limited in this respect.
In a preferred embodiment, in step (c), the mass ratio of the zirconium source in the zirconium dioxide sol to the phenolic resin in the phenolic resin solution is from 1:20 to 1:5, preferably from 1:15 to 1: 8. The above mass ratio is typically, but not limited to, 1:20, 1:19, 1:18, 1:17, 1:16, 1:15, 1:14, 1:13, 1:12, 1:11, 1:10, 1:9, 1:8, 1:7, 1:6 or 1: 5. When the mass ratio of the zirconium source to the phenolic resin is in the range, the ratio of zirconium dioxide to phenolic resin in the aerogel can be controlled in a more reasonable range, and the performance of the aerogel is further improved.
Preferably, in step (c), the curing agent comprises at least one of hexamethylenetetramine, aniline, melamine or melamine resin. Typical but non-limiting examples of such curing agents are hexamethylenetetramine, aniline, melamine resin, a combination of hexamethylenetetramine and melamine, a combination of aniline and melamine resin, or a combination of hexamethylenetetramine, aniline and melamine, and the like. The melamine resin is also called melamine formaldehyde resin, and refers to a polymer obtained by polymerizing melamine and formaldehyde. The curing agent has high compatibility with a zirconium source and phenolic aldehyde, and can accelerate the curing of phenolic resin and promote the sol-gel reaction.
Preferably, in the step (c), the zirconium dioxide sol in the step (a) and the phenolic resin solution in the step (b) are uniformly mixed, and then are mixed with the curing agent until a clear and transparent solution is obtained.
Preferably, in step (c), the mass ratio of the phenolic resin to the curing agent is 3:1 to 10:1, preferably 4:1 to 8: 1. The above mass ratio is typically, but not limited to, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10: 1.
Optionally, in the step (c), after the zirconium dioxide sol in the step (a) and the phenolic resin solution in the step (b) are uniformly mixed, mixing with a curing agent until a clear and transparent solution is obtained. Optionally, the time for mixing with the curing agent is 30-60 min. The mixing time is typically, but not limited to, 30min, 32min, 34min, 36min, 38min, 40min, 42min, 44min, 46min, 48min, 50min, 52min, 54min, 56min, 58min, or 60 min.
Preferably, in step (d), the aging time is 2 to 7 days. Such aging times are typically, but not limited to, 2 days, 2.5 days, 3 days, 3.5 days, 4 days, 4.5 days, 5 days, 5.5 days, 6 days, 6.5 days, or 7 days. The gel polymer can be promoted to be further polymerized and wound after aging, and the strength of the wet gel is improved.
Preferably, in step (d), the drying comprises atmospheric drying; preferably, the drying under atmospheric pressure comprises first drying at 20-30 deg.C for 1-3 days, and then drying at 50-80 deg.C for 1-2 days. The specific process is adopted for drying, so that the wet gel can be quickly dehydrated to form dry gel, and the process is simpler compared with complex processes such as supercritical drying and the like.
Alternatively, the clear transparent solution can be placed in a metal mold, particularly a stainless steel mold, and sealed for sol-gel reaction.
According to another aspect of the present invention, there is provided a use of the aerogel described above in a high temperature insulation material or a lightweight insulation material. The aerogel is applied to high-temperature heat insulation materials or light heat prevention/insulation materials, so that the strength, high-temperature heat insulation and heat prevention effects of the material can be obviously improved, and the application field of the material is expanded. The above-mentioned "lightweight heat prevention/insulation material" means a material which is lightweight and has heat prevention and/or insulation properties.
According to another aspect of the present invention, there is provided a high temperature insulation material or a lightweight heat/insulation material comprising the aerogel described above. The high-temperature heat insulating material or the light weight heat preventing/insulating material comprises the aerogel, so that the aerogel has at least the same advantages as the aerogel, and has the advantages of light weight, high strength, high temperature resistance and ablation resistance.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium acetate, adding the zirconium acetate into methanol to prepare a solution with the mass fraction of 10%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 1000, adding the phenolic resin into a reaction kettle containing a certain amount of methanol, controlling the mass concentration of the phenolic resin to be 30%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, and adding a certain amount of melamine, wherein the mass ratio of the phenolic resin to the melamine is 4: 1; obtaining a clear and transparent solution after the melamine is completely dissolved; the mass ratio of the zirconium acetate to the phenolic resin is 1: 8;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution just prepared is yellow, and the water bath reaction is aged for 5 days, and the color gradually deepens in the period; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and drying in an oven at 100 ℃ for 1 day to obtain the aerogel.
The density of the aerogel was found to be 0.43g/cm3A compressive strength of 35MPa and a thermal conductivity at room temperature of 0.05W (m.K)-1。
Example 2
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium oxychloride, adding the zirconium oxychloride into methanol to prepare a solution with the mass fraction of 5%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 1200, adding the phenolic resin into a reaction kettle containing a certain amount of methanol, controlling the mass concentration of the phenolic resin to be 20%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, and adding a certain amount of hexamethylenetetramine, wherein the mass ratio of the phenolic resin to the hexamethylenetetramine is 5: 1; obtaining a clear and transparent solution after the hexamethylenetetramine is completely dissolved; the mass ratio of the zirconium oxychloride to the phenolic aldehyde is 1: 7;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution which is just prepared is yellow, and the water bath reaction is aged for 5 days, and the color is gradually darker; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and drying in an oven at 70 ℃ for 3 days to obtain the aerogel.
The density of the aerogel was measured to be 0.28g/cm3Compressive strength of 26MPa, room temperature thermal conductivity of 0.04W (m.K)-1。
Example 3
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium isopropoxide, adding the zirconium isopropoxide into ethanol to prepare a solution with the mass fraction of 5%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 1500, adding the phenolic resin into a reaction kettle containing a certain amount of ethanol, controlling the mass concentration of the phenolic resin to be 25%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, and adding a certain amount of hexamethylenetetramine, wherein the mass ratio of the phenolic resin to the hexamethylenetetramine is 6: 1; obtaining a clear and transparent solution after the hexamethylenetetramine is completely dissolved; the mass ratio of the zirconium isopropoxide to the phenolic resin is 1: 5;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution which is just prepared is yellow, and the water bath reaction is aged for 4 days, and the color gradually deepens in the period; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and drying in an oven at 80 ℃ for 3 days to obtain the aerogel.
The density of the aerogel was measured to be 0.32g/cm3Compressive strength of 30MPa, room temperature thermal conductivity of 0.04W (m.K)-1。
Example 4
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium acetate, adding the zirconium acetate into ethanol to prepare a solution with the mass fraction of 20%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 500, adding the phenolic resin into a reaction kettle containing a certain amount of ethanol, controlling the mass concentration of the phenolic resin to be 25%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, and adding a certain amount of aniline, wherein the mass ratio of the phenolic resin to the aniline is 7: 1; obtaining a clear and transparent solution after aniline is completely dissolved; the mass ratio of the zirconium acetate to the phenolic resin is 1: 5;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution which is just prepared is yellow, and the water bath reaction is aged for 4 days, and the color gradually deepens in the period; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and drying in an oven at 80 ℃ for 3 days to obtain the aerogel.
The density of the aerogel was found to be 0.30g/cm3Compressive strength of 28MPa, room temperature thermal conductivity of 0.04W (m.K)-1。
Example 5
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium isopropoxide, adding the zirconium isopropoxide into isopropanol to prepare a solution with the mass fraction of 10%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 1500, adding the phenolic resin into a reaction kettle containing a certain amount of isopropanol, controlling the mass concentration of the phenolic resin to be 15%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, adding a certain amount of aniline, wherein the mass ratio of the phenolic resin to the aniline is 7:1, and obtaining a clear transparent solution after the aniline is completely dissolved; the mass ratio of the zirconium isopropoxide to the phenolic resin is 1: 5;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution which is just prepared is yellow, and the water bath reaction is aged for 4 days, and the color gradually deepens in the period; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and drying in an oven at 90 ℃ for 2 days to obtain the aerogel.
The aerogel density was found to be 0.18g/cm3Compressive strength of 10MPa, room temperature thermal conductivity of 0.03W (m.K)-1。
Example 6
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium isopropoxide, adding the zirconium isopropoxide into methanol to prepare a solution with the mass fraction of 5%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 1500, adding the phenolic resin into a reaction kettle containing a certain amount of methanol, controlling the mass concentration of the phenolic resin to be 20%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, and adding a certain amount of hexamethylenetetramine, wherein the mass ratio of the phenolic resin to the hexamethylenetetramine is 8: 1; obtaining a clear and transparent solution after the hexamethylenetetramine is completely dissolved;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution which is just prepared is yellow, and the water bath reaction is aged for 2 days, and the color is gradually darker; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and drying in an oven at 80 ℃ for 2 days to obtain the aerogel.
The density of the aerogel was found to be 0.27g/cm3Compressive strength of 25MPa, room temperature thermal conductivity of 0.04W (m.K)-1。
Example 7
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium oxychloride, adding the zirconium oxychloride into methanol to prepare a solution with the mass fraction of 20%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 1500, adding the phenolic resin into a reaction kettle containing a certain amount of methanol, controlling the mass concentration of the phenolic resin to be 45%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, and adding a certain amount of melamine, wherein the mass ratio of the phenolic resin to the melamine is 6: 1; obtaining a clear and transparent solution after the melamine is completely dissolved; the mass ratio of the zirconium oxychloride to the phenolic resin is 1: 8;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution which is just prepared is yellow, and the water bath reaction is aged for 3 days, and the color is gradually darker; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and drying in an oven at 100 ℃ for 2 days to obtain the aerogel.
The aerogel density was found to be 0.59g/cm3A compressive strength of 55MPa and a thermal conductivity at room temperature of 0.07W (m.K)-1。
Example 8
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium oxychloride, adding the zirconium oxychloride into methanol to prepare a solution with the mass fraction of 20%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 1500, adding the phenolic resin into a reaction kettle containing a certain amount of methanol, controlling the mass concentration of the phenolic resin to be 45%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, and adding a certain amount of melamine, wherein the mass ratio of the phenolic resin to the melamine is 4: 1; obtaining a clear and transparent solution after the melamine is completely dissolved; the mass ratio of zirconium oxychloride to phenolic resin is 1: 3;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution which is just prepared is yellow, and the water bath reaction is aged for 2 days, and the color is gradually darker; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and then drying in an oven at 120 ℃ for 3 days to obtain the aerogel.
The aerogel density was found to be 0.58g/cm3A compressive strength of 55MPa and a thermal conductivity at room temperature of 0.06W (m.K)-1。
Example 9
An aerogel prepared by the following method:
(a) weighing a certain amount of zirconium isopropoxide, adding the zirconium isopropoxide into methanol to prepare a solution with the mass fraction of 10%, and stirring for 10min to obtain uniform zirconium dioxide sol for later use;
(b) weighing a certain amount of phenolic resin with the weight average molecular weight of 2000, adding the phenolic resin into a reaction kettle containing a certain amount of methanol, controlling the mass concentration of the phenolic resin to be 20%, and mechanically stirring until the phenolic resin is completely dissolved to obtain a phenolic resin solution;
(c) uniformly mixing and stirring zirconium dioxide sol and a phenolic resin solution, and adding a certain amount of melamine, wherein the mass ratio of the phenolic resin to the melamine is 6: 1; obtaining a clear and transparent solution after the melamine is completely dissolved; the mass ratio of the zirconium isopropoxide to the phenolic resin is 1: 10;
(d) sealing the clear transparent solution in a regular container, placing the container in a constant-temperature water bath at the temperature of 100 ℃ for sol-gelation reaction, wherein the solution which is just prepared is yellow, and the water bath reaction is aged for 3 days, and the color is gradually darker; and finally, taking out the wet gel, drying for 2 days at normal temperature and normal pressure, and drying in an oven at 90 ℃ for 3 days to obtain the aerogel.
The aerogel density was found to be 0.29g/cm3Compressive strength of 26MPa, room temperature thermal conductivity of 0.04W (m.K)-1。
Comparative example 1
An aerogel prepared by the following method:
weighing a certain amount of phenolic resin with the weight average molecular weight of 500 and hexamethylenetetramine, wherein the mass ratio of the phenolic resin to the hexamethylenetetramine is 4:1, adding the phenolic resin and the hexamethylenetetramine into a reaction kettle containing a certain amount of ethanol, controlling the mass concentration of the phenolic resin to be 15%, and mechanically stirring until the phenolic resin and the hexamethylenetetramine are completely dissolved to obtain a phenolic resin solution. And sealing the phenolic resin-hexamethylenetetramine mixed ethanol solution in a regular container, and placing the container in a constant-temperature water bath at the temperature of 80 ℃ to perform sol-gelation reaction, wherein the solution which is just prepared is light yellow, and the water bath reaction is aged for 6 days, and the color gradually deepens in the period. And finally, taking out the wet gel, drying for 1 day at normal temperature and normal pressure, and then drying in an oven at 80 ℃ for 1 day to obtain the organic aerogel.
The density of the organic aerogel was found to be 0.17g/cm3。
Comparative example 2
CN109200955A the organic-inorganic dual-network structure phenolic/alumina aerogel composite material in example 1.
The density was found to be 0.28g/cm3The compressive strength was 0.82 MPa.
The comprehensive performance of the aerogel in each embodiment is superior to that of each proportion, so that the aerogel and the preparation method thereof provided by the invention are scientific and reasonable, the aerogel has the ablation and heat insulation integrated function, the preparation process is simple, and the cost is low.
As shown in FIG. 1, which is the infrared spectra of the aerogel in example 3 (Zr-PF in the figure) and comparative example 1 (PF in the figure), it can be seen that the positions of the main absorption characteristic peaks are substantially the same in the infrared spectra before and after hybridization: at 3400cm-1A stretching vibration absorption peak of-OH appears; 1600cm-1And 1500cm-1Is a characteristic peak of a benzene ring skeleton; 1226cm-1Is the absorption peak of the phenolic hydroxyl group; 1100cm-1The absorption peak is the absorption peak of the benzylic hydroxyl C-O bond. At 495cm-1The absorption peak at (a) corresponds to the Zr — O bond in the hybrid aerogel, and this peak is not present in the ir spectrum of the unhybridized aerogel. The above results show that the high molecular phenolic resin chain has been successfully grafted with zirconium element.
Fig. 2 shows scanning electron micrographs of aerogels in examples 3 to 5 and comparative example 1 (wherein (a) in fig. 2 is the aerogel of comparative example 1, and (b) to (d) in fig. 2 are the aerogels of examples 3 to 5, respectively), and it can be seen from the images that the prepared aerogel particles form a microstructure having a three-dimensional network, and the aerogel particles have a micro-scale macroporous structure.
FIG. 3 shows thermogravimetric graphs of aerogels in examples 3-5 and comparative example 1 (wherein Zr-PF-0 is the aerogel of comparative example 1, Zr-PF-5 is the aerogel of example 3, Zr-PF-10 is the aerogel of example 5, and Zr-PF-20 is the aerogel of example 4), and it can be seen from the graphs that the thermal weight loss curves of the aerogels in the examples are similar to those of the aerogel in comparative example 1, and the thermal weight loss curves are divided into three distinct stages: a stage of a minor loss of mass at a temperature within 400 ℃; an intermediate stage with serious mass loss at 400-700 ℃; a high temperature stage with a small mass loss above 700 ℃. When the temperature is lower than 400 ℃, the thermal weight loss curves of the four aerogels are basically consistent, and when the temperature is higher than 400 ℃, the aerogels of the embodiments can keep higher mass residual quantity, which shows that the introduction of zirconium can improve the thermal stability of the aerogels, especially the thermal stability at high temperature of more than 400 ℃.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (17)
1. The preparation method of the aerogel is characterized by comprising the following steps: mixing phenolic resin, a zirconium source, a curing agent and a solvent, and then sequentially carrying out sol-gel reaction, aging and drying to obtain the aerogel.
2. Method for the preparation of aerogels according to claim 1, characterized in that it comprises the following steps:
(a) preparing zirconium dioxide sol: mixing a zirconium source and a solvent;
(b) preparing a phenolic resin solution: mixing phenolic resin and a solvent;
(c) uniformly mixing the zirconium dioxide sol in the step (a), the phenolic resin solution in the step (b) and a curing agent until a clear transparent solution is obtained;
(d) and (c) carrying out sol-gel reaction on the clear transparent solution obtained in the step (c) under the conditions of sealing and 60-180 ℃, and then aging and drying to obtain the aerogel.
3. A method of producing aerogels according to claim 2 wherein in step (a) the source of zirconium comprises at least one of zirconium acetate, zirconium oxychloride or zirconium isopropoxide.
4. The method for preparing an aerogel according to claim 2, wherein in the step (a), the content of the zirconium source in the zirconia sol is 5 to 20% by mass.
5. The method for preparing aerogel according to claim 2, wherein in step (b), the weight average molecular weight of the phenolic resin is 500-2000.
6. The method for preparing the aerogel according to claim 2, wherein in the step (b), the mass percentage of the phenolic resin in the phenolic resin solution is 5-60%.
7. The method for preparing an aerogel according to claim 2, wherein the solvent in step (a) and/or (b) comprises an alcohol.
8. The method for the preparation of aerogels according to claim 7, characterised in that said alcohols comprise alcohols from C1 to C4.
9. The method of preparing an aerogel of claim 7, wherein the alcohol comprises at least one of methanol, ethanol, or isopropanol.
10. The method for preparing an aerogel according to claim 2, wherein in step (c), the mass ratio of the zirconium source in the zirconium dioxide sol to the phenolic resin in the phenolic resin solution is 1:20 to 1: 5.
11. The method for preparing aerogel according to claim 2, wherein the curing agent in step (c) comprises at least one of hexamethylenetetramine, aniline, melamine or melamine resin.
12. The method for preparing aerogel according to claim 2, wherein in the step (c), the mass ratio of the phenolic resin to the curing agent is 3:1-10: 1.
13. The method for preparing an aerogel according to any of claims 1 to 12, wherein the aging time in step (d) is 2 to 7 days.
14. The method for preparing an aerogel according to any of claims 1 to 12, wherein the drying in step (d) comprises atmospheric drying.
15. The method for preparing aerogel according to claim 14, wherein the drying under normal pressure comprises drying at 20-30 ℃ for 1-3 days first, and then drying at 50-80 ℃ for 1-2 days.
16. Use of the aerogel obtained by the method of any one of claims 1 to 15 in high temperature insulation or lightweight insulation/protection materials.
17. A high temperature thermal insulation material or lightweight thermal/insulation material comprising an aerogel produced by the method of any of claims 1 to 15.
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