CN109320882B - Silica-modified PVDF aerogel, preparation method and aerogel product comprising same - Google Patents
Silica-modified PVDF aerogel, preparation method and aerogel product comprising same Download PDFInfo
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- CN109320882B CN109320882B CN201811310277.9A CN201811310277A CN109320882B CN 109320882 B CN109320882 B CN 109320882B CN 201811310277 A CN201811310277 A CN 201811310277A CN 109320882 B CN109320882 B CN 109320882B
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- 239000004964 aerogel Substances 0.000 title claims abstract description 120
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 78
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 230000032683 aging Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000004115 Sodium Silicate Substances 0.000 claims description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 abstract description 23
- 239000003513 alkali Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 8
- 239000012774 insulation material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003989 dielectric material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004965 Silica aerogel Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000011172 small scale experimental method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
Classifications
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a silicon dioxide modified PVDF aerogel, a preparation method and an aerogel product comprising the silicon dioxide modified PVDF aerogel, and relates to the technical field of dielectric materials. Dissolving vinylidene fluoride in an organic solution, adding a precursor silicon source, uniformly mixing to obtain a precursor solution, hydrolyzing the precursor solution to obtain a precursor sol, standing and aging, and then performing solvent replacement and drying on the aged precursor sol to obtain the silicon dioxide modified PVDF aerogel. Due to the fact that the polyvinylidene fluoride is added in the preparation process, the structure of PVDF (polyvinylidene fluoride) is formed in the internal structure of the aerogel, and the polyvinylidene fluoride has good high temperature resistance and acid and alkali resistance, the high temperature resistance and the acid and alkali resistance of the aerogel material can be remarkably improved, and the requirement that the aerogel is used as a heat insulation material in the prior art under the environment with high temperature and complex chemical components is met.
Description
Technical Field
The invention relates to the technical field of dielectric materials, in particular to a silicon dioxide modified PVDF aerogel, a preparation method and an aerogel product comprising the silicon dioxide modified PVDF aerogel.
Background
The aerogel has the characteristics of low density, high specific surface area, high porosity and the like, and is known as a magic material for changing the world. Because of a large number of nano-scale holes in the aerogel, the aerogel has excellent heat insulation performance, is a solid material with extremely low heat conductivity coefficient, has the heat conductivity coefficient of about 0.013W/(m.K) at normal temperature, and is lower than that of static air. Meanwhile, the aerogel also has the characteristics of high stability, environmental friendliness and the like, has a good hydrophobic effect after modification, and has a huge application prospect in the low-temperature cold insulation fields of Liquefied Natural Gas (LNG) pipelines, storage tanks, ships and the like.
However, the density of the aerogel is very low and is only 0.03-0.38g/cc, and in addition, the aerogel has over 95 percent of porosity, the nanometer-scale pore size is filled with gas, and the structural characteristics are particularly suitable for heat insulation and heat preservation, wherein: the low density and air-filled pores can reduce energy loss by conduction, and the curved nano-scale pores can minimize convection. Although the aerogel has the excellent properties, the low density and high porosity of the aerogel itself cause the aerogel to have very low mechanical strength and easy breakage, thereby limiting the application range of the aerogel in small-scale experiments and basic researches, such as the application of the aerogel as a heat insulation and preservation material in special fields, the high temperature resistance and the acid and alkali resistance of the aerogel must be improved.
Therefore, it is necessary and urgent to develop an aerogel product that can significantly improve the high temperature resistance and the acid and alkali resistance of an aerogel material while maintaining the excellent properties of the aerogel, so as to meet the requirements of the prior art that the aerogel is used as a thermal insulation material in the environment with high temperature and complicated chemical components.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a silicon dioxide modified PVDF aerogel, wherein a PVDF (polyvinylidene fluoride) structure is formed in the internal structure of the aerogel in the preparation process of the aerogel, and the polyvinylidene fluoride has very good high temperature resistance and acid and alkali resistance, so that the high temperature resistance and acid and alkali resistance of the aerogel material can be remarkably improved, and the requirement of the existing aerogel as a heat insulation material in the environment with complex high temperature and chemical components can be further met.
The second purpose of the invention is to provide a silica modified PVDF aerogel, which is prepared by the preparation method of the silica modified PVDF aerogel, and the high temperature resistance of the silica modified PVDF aerogel prepared by the method can reach not less than 300 ℃, and the specific surface area is 300-700 m2The thermal conductivity coefficient is less than or equal to 0.03W/(m.K), and the coating has good acid and alkali resistance.
A third object of the present invention is to provide an aerogel product comprising the above silica-modified PVDF aerogel, including but not limited to aerogel blanket and the like.
The invention provides a preparation method of a silicon dioxide modified PVDF aerogel, which comprises the following steps:
firstly, dissolving vinylidene fluoride in an organic solution, adding a precursor silicon source, uniformly mixing to prepare a precursor solution, hydrolyzing the precursor solution to prepare a precursor sol, standing and aging, and then carrying out solvent replacement and drying on the aged precursor sol to prepare the silicon dioxide modified PVDF aerogel.
Further, the organic solution is any one of dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
Preferably, the precursor silicon source is ethyl orthosilicate or sodium silicate solution.
Furthermore, the mass ratio of the vinylidene fluoride to the organic solution to the precursor silicon source is 1 (5-8) to 1-1.5.
Further, the method for hydrolyzing the precursor solution comprises the following steps: under the condition of stirring, adding water into the precursor solution in a dropwise manner;
furthermore, the mass ratio of the precursor solution to water is 4-6: 1;
preferably, the dropping speed is 6-8 ml/min.
Further, the temperature of standing and aging is 10-30 ℃, and the time is 20-30 min.
Further, the solvent replacement is to place the aged precursor sol in alcohol or deionized water for solvent replacement;
preferably, the number of times of solvent replacement is 4-8, and the replacement time is 8-10 h each time.
Further, the drying temperature is 120-200 ℃.
The invention provides a silicon dioxide modified PVDF aerogel, which is prepared by the preparation method of the silicon dioxide modified PVDF aerogel.
The invention provides an aerogel product, which comprises the silicon dioxide modified PVDF aerogel.
Compared with the prior art, the invention has the beneficial effects that:
dissolving vinylidene fluoride in an organic solution, adding a precursor silicon source, uniformly mixing to obtain a precursor solution, hydrolyzing the precursor solution to obtain a precursor sol, standing and aging, and then performing solvent replacement and drying on the aged precursor sol to obtain the silicon dioxide modified PVDF aerogel. Due to the fact that the vinylidene fluoride is added into the aerogel in the preparation process, a structure of PVDF (polyvinylidene fluoride) is formed in the internal structure of the aerogel, and the polyvinylidene fluoride has good high temperature resistance and acid and alkali resistance, the high temperature resistance and the acid and alkali resistance of the aerogel material can be remarkably improved, and the requirement that the aerogel is used as a heat insulation material in the prior art under the environment with high temperature and complex chemical components is met.
The silica modified PVDF aerogel provided by the invention is prepared by the preparation method of the silica modified PVDF aerogel, and the high temperature resistance of the silica modified PVDF aerogel prepared by the method can reach not less than 300 ℃, and the specific surface area is 300-700 m2The thermal conductivity coefficient is less than or equal to 0.03W/(m.K), and the coating has good acid and alkali resistance.
The aerogel products provided by the present invention include the silica modified PVDF aerogel described above, including but not limited to aerogel blankets and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the present invention, a method for preparing a silica-modified PVDF aerogel, the method comprising the steps of:
firstly, dissolving vinylidene fluoride in an organic solution, adding a precursor silicon source, uniformly mixing to prepare a precursor solution, hydrolyzing the precursor solution to prepare a precursor sol, standing and aging, and then carrying out solvent replacement and drying on the aged precursor sol to prepare the silicon dioxide modified PVDF aerogel.
Dissolving vinylidene fluoride in an organic solution, adding a precursor silicon source, uniformly mixing to obtain a precursor solution, hydrolyzing the precursor solution to obtain a precursor sol, standing and aging, and then performing solvent replacement and drying on the aged precursor sol to obtain the silicon dioxide modified PVDF aerogel. Due to the fact that the vinylidene fluoride is added into the aerogel in the preparation process, a structure of PVDF (polyvinylidene fluoride) is formed in the internal structure of the aerogel, and the polyvinylidene fluoride has good high temperature resistance and acid and alkali resistance, the high temperature resistance and the acid and alkali resistance of the aerogel material can be remarkably improved, and the requirement that the aerogel is used as a heat insulation material in the prior art under the environment with high temperature and complex chemical components is met.
In a preferred embodiment of the present invention, the organic solution is any one of dimethylformamide, dimethylacetamide, or dimethylsulfoxide.
As a preferred embodiment, the dimethylformamide, dimethylacetamide or dimethylsulfoxide can make vinylidene fluoride sufficiently dissolved in the organic solution, and further make the inside of the aerogel of the present application form a structure of PVDF (polyvinylidene fluoride) through a polymerization reaction in a later hydrolysis process.
In a preferred embodiment of the present invention, the precursor silicon source is ethyl orthosilicate or a sodium silicate solution.
As a preferred embodiment, the above-mentioned ethyl orthosilicate or sodium silicate solution is used as a precursor silicon source to form the silica aerogel.
Preferably, the solvent of the sodium silicate solution is ethanol, and the content of the sodium silicate is 10-20 wt%.
In a preferred embodiment of the present invention, the mass ratio of the vinylidene fluoride, the organic solution and the precursor silicon source is 1 (5-8) to 1-1.5.
In a preferred embodiment of the present invention, the precursor solution is hydrolyzed by the following steps: under the condition of stirring, adding water into the precursor solution in a dropwise manner;
in the above preferred embodiment, the mass ratio of the precursor solution to water is 5: 1;
more preferably, the dropping speed is 6-8 ml/min.
In a preferred embodiment of the invention, the temperature of the standing and aging is 10-30 ℃ and the time is 20-30 min.
In the present invention, the temperature for the standing aging is typically, but not limited to, 10 ℃, 15 ℃, 20 ℃, 25 ℃ and 30 ℃.
In a preferred embodiment of the present invention, the solvent replacement is to place the aged precursor sol in alcohol or deionized water for solvent replacement;
preferably, the number of times of solvent replacement is 4-8, and the replacement time is 8-10 h each time.
In a preferred embodiment of the present invention, the drying temperature is 120 to 200 ℃.
According to one aspect of the invention, a silica-modified PVDF aerogel is prepared by the preparation method of the silica-modified PVDF aerogel.
The silica modified PVDF aerogel provided by the invention is prepared by the preparation method of the silica modified PVDF aerogel, and the high temperature resistance of the silica modified PVDF aerogel prepared by the method can reach not less than 300 ℃, and the specific surface area is 300-700 m2The thermal conductivity coefficient is less than or equal to 0.03W/(m.K), and the coating has good acid and alkali resistance.
According to one aspect of the invention, an aerogel article comprises the silica-modified PVDF aerogel described above.
The aerogel products provided by the present invention include the silica modified PVDF aerogel described above, including but not limited to aerogel blankets and the like.
The technical solution of the present invention will be further described with reference to examples and comparative examples.
Example 1
A method for preparing a silica-modified PVDF aerogel, the method comprising the steps of:
(1) dissolving vinylidene fluoride into dimethylformamide, adding tetraethoxysilane, and uniformly mixing to prepare a precursor solution, wherein the mass ratio of the vinylidene fluoride to the dimethylformamide to the tetraethoxysilane is 1:5: 1.
(2) Under the condition of stirring, adding water into the precursor solution in a dropwise manner for hydrolysis to prepare precursor sol, wherein the mass ratio of the precursor solution to the water is 5:1, the dropping rate is 6 ml/min.
(3) Standing and aging the precursor sol for 20min at the temperature of 10 ℃, then placing the aged and molded precursor sol in deionized water for solvent replacement for 4 times, wherein the replacement time is 8h each time, and finally drying at the temperature of 120 ℃ to prepare the silicon dioxide modified PVDF aerogel.
Example 2
A method for preparing a silica-modified PVDF aerogel, the method comprising the steps of:
(1) firstly, dissolving vinylidene fluoride in dimethylacetamide, adding sodium silicate solution, uniformly mixing to prepare precursor solution,
the mass ratio of the vinylidene fluoride to the dimethylacetamide to the sodium silicate solution is 1:8: 1.5;
the solvent of the sodium silicate solution is ethanol, and the content of the sodium silicate is 10 wt%.
(2) Under the condition of stirring, adding water into the precursor solution in a dropwise manner for hydrolysis to prepare precursor sol, wherein the mass ratio of the precursor solution to the water is 5:1, the dropping rate is 8 ml/min.
(3) Standing and aging the precursor sol for 30min at the temperature of 30 ℃, then placing the aged and molded precursor sol in deionized water for solvent replacement for 8 times, wherein the replacement time is 10h each time, and finally drying at the temperature of 200 ℃ to prepare the silicon dioxide modified PVDF aerogel.
Example 3
A method for preparing a silica-modified PVDF aerogel, the method comprising the steps of:
(1) firstly, dissolving vinylidene fluoride in dimethyl sulfoxide, adding tetraethoxysilane, and uniformly mixing to prepare a precursor solution, wherein the mass ratio of the vinylidene fluoride to the dimethyl sulfoxide to the tetraethoxysilane is 1:6: 1.2.
(2) Under the condition of stirring, adding water into the precursor solution in a dropwise manner for hydrolysis to prepare precursor sol, wherein the mass ratio of the precursor solution to the water is 5:1, the dropping rate is 7 ml/min.
(3) Standing and aging the precursor sol for 22min at 15 ℃, then placing the aged and molded precursor sol in deionized water for solvent replacement for 5 times, wherein the replacement time is 9h each time, and finally drying at 150 ℃ to prepare the silicon dioxide modified PVDF aerogel.
Example 4
A method for preparing a silica-modified PVDF aerogel, the method comprising the steps of:
(1) dissolving vinylidene fluoride into dimethylformamide, adding a sodium silicate solution, and uniformly mixing to obtain a precursor solution, wherein the mass ratio of the vinylidene fluoride to the dimethylformamide to the sodium silicate solution is 1:7: 1.4.
The solvent of the sodium silicate solution is ethanol, and the content of the sodium silicate is 20 wt%.
(2) Under the condition of stirring, adding water into the precursor solution in a dropwise manner for hydrolysis to prepare precursor sol, wherein the mass ratio of the precursor solution to the water is 5:1, the dropping rate is 6 ml/min.
(3) Standing and aging the precursor sol for 28min at the temperature of 18 ℃, then placing the aged and molded precursor sol in deionized water for solvent replacement for 7 times, wherein the replacement time is 10h each time, and finally drying at the temperature of 180 ℃ to obtain the silicon dioxide modified PVDF aerogel.
Example 5
A method for preparing a silica-modified PVDF aerogel, the method comprising the steps of:
(1) dissolving vinylidene fluoride in dimethylacetamide, adding a sodium silicate solution, and uniformly mixing to prepare a precursor solution, wherein the mass ratio of the vinylidene fluoride to the dimethylacetamide to the sodium silicate solution is 1:6: 1.3;
the solvent of the sodium silicate solution is ethanol, and the content of the sodium silicate is 15 wt%.
(2) Under the condition of stirring, adding water into the precursor solution in a dropwise manner for hydrolysis to prepare precursor sol, wherein the mass ratio of the precursor solution to the water is 5:1, the dropping rate is 7 ml/min.
(3) Standing and aging the precursor sol for 25min at the temperature of 20 ℃, then placing the aged and molded precursor sol in deionized water for solvent replacement for 6 times, wherein the replacement time is 9h each time, and finally drying at the temperature of 160 ℃ to prepare the silicon dioxide modified PVDF aerogel.
Comparative example 1
This comparative example is the same as example 5 except that it was prepared without the inclusion of vinylidene fluoride.
Comparative example 2
The comparative example is the same as example 5 except that the mass ratio of the vinylidene fluoride, the dimethylformamide and the sodium silicate solution in the precursor solution in the step (1) is 0.8:6: 1.3.
Comparative example 3
The mass ratio of the precursor solution in the step (2) to water in the comparative example is 3: 1, the same as example 5.
Experimental example 1
In order to show that the silica modified PVDF aerogel prepared by the invention has the advantages of high temperature resistance, acid and alkali resistance, large specific surface area and good thermal conductivity, the silica modified PVDF aerogels prepared in the embodiments 1 to 5 and the comparative examples 1 to 3 of the invention are particularly subjected to the detection of high temperature resistance, acid and alkali resistance, specific surface area and thermal conductivity, and the results are shown in the following table 1.
(1) High temperature test
Placing the aerogel on a test board, placing the test board in an environment at 300 ℃ for 10 days, and observing the change condition of the aerogel.
(2) And (3) acid and alkali resistance test:
the aerogel is placed on a test board, the test board is placed in an acid and alkali solution at 25 ℃ for 30 days, and the erosion condition of the aerogel is observed.
(3) Specific surface area (m)2/g)
The measurement was carried out using a specific surface pore size analyzer model SPECTOMER 1990 manufactured by thermoelectricity corporation, USA.
(4) Thermal conductivity [ W/(m.K) ]
Thermal conductivity was measured using a model STA449C thermal conductivity tester pair. The operation method comprises the following steps: the prepared aerogel is ground into superfine powder, and the powder with the thickness of about 1cm is laid on a probe (the sample support has small volume and is not required to be compacted), so that the heat conductivity coefficient can be measured.
Table 1: performance test results of silica-modified PVDF aerogels prepared in examples and comparative examples
As can be seen from Table 1, the silicon dioxide modified PVDF aerogel prepared in the embodiments 1 to 5 of the invention has the high temperature resistance of not less than 300 ℃, no change after being placed in an environment of 300 ℃ for 10 days, the specific surface area of 300 to 700m2/g, the thermal conductivity of not more than 0.03W/(m.K), and good acid and alkali resistance, and the high temperature resistance, the acid and alkali resistance, the specific surface area and the thermal conductivity of the silicon dioxide modified PVDF aerogel are superior to those of the silicon dioxide modified PVDF aerogel prepared in the comparative examples 1 to 3
The silicon dioxide modified PVDF aerogel which does not contain the vinylidene fluoride in the comparative example 1 does not have the performances of high temperature resistance and acid and alkali resistance; in the comparative example 2, the content of vinylidene fluoride in the precursor solution is low, so that the prepared silicon dioxide modified PVDF aerogel has poor high temperature resistance, acid and alkali resistance, and also has poor specific surface area and thermal conductivity coefficient; in the hydrolysis process of the comparative example 3, the hydrolysis is not complete due to the lower mass ratio of the precursor solution to water, and various properties of the prepared silicon dioxide modified PVDF aerogel can not meet corresponding requirements.
In summary, the preparation method of the silica modified PVDF aerogel provided by the invention comprises the steps of dissolving vinylidene fluoride in an organic solution, adding a precursor silicon source, uniformly mixing to obtain a precursor solution, hydrolyzing the precursor solution to obtain a precursor sol, and then sequentially standing, aging, solvent replacing and drying the precursor sol to obtain the silica modified PVDF aerogel. Due to the fact that the vinylidene fluoride is added into the aerogel in the preparation process, a structure of PVDF (polyvinylidene fluoride) is formed in the internal structure of the aerogel, and the polyvinylidene fluoride has good high temperature resistance and acid and alkali resistance, the high temperature resistance and the acid and alkali resistance of the aerogel material can be remarkably improved, and the requirement that the aerogel is used as a heat insulation material in the prior art under the environment with high temperature and complex chemical components is met.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. A preparation method of a silica modified PVDF aerogel is characterized by comprising the following steps:
firstly, dissolving vinylidene fluoride in an organic solution, adding a precursor silicon source, uniformly mixing to prepare a precursor solution, hydrolyzing the precursor solution to prepare a precursor sol, standing and aging, and then carrying out solvent replacement and drying on the aged precursor sol to prepare the silicon dioxide modified PVDF aerogel;
the mass ratio of the vinylidene fluoride to the organic solution to the precursor silicon source is 1 (5-8) to 1-1.5;
the mass ratio of the precursor solution to water is 4-5: 1.
2. the method for preparing a silica-modified PVDF aerogel according to claim 1, wherein the organic solution is any one of dimethylformamide, dimethylacetamide, or dimethylsulfoxide.
3. The method for preparing the silica-modified PVDF aerogel according to claim 1, wherein the precursor silicon source is ethyl orthosilicate or sodium silicate solution.
4. The method for preparing a silica-modified PVDF aerogel according to claim 1, wherein the precursor solution is hydrolyzed by: under the condition of stirring, water is added into the precursor solution in a dropwise manner.
5. The method for preparing the silica-modified PVDF aerogel according to claim 4, wherein the dropping rate is 6-8 ml/min.
6. The method for preparing the silica-modified PVDF aerogel according to claim 1, wherein the temperature of standing and aging is 10-30 ℃ for 20-30 min.
7. The method for preparing the silica-modified PVDF aerogel according to claim 1, wherein the solvent replacement is performed by placing the aged precursor sol in alcohol or deionized water.
8. The method for preparing the silica-modified PVDF aerogel according to claim 7, wherein the number of times of solvent replacement is 4-8, and the time of each replacement is 8-10 h.
9. The method for preparing the silica-modified PVDF aerogel according to claim 1, wherein the drying temperature is 120-200 ℃.
10. The silica-modified PVDF aerogel is characterized by being prepared by the preparation method of the silica-modified PVDF aerogel as described in any one of claims 1-9.
11. An aerogel article comprising the silica-modified PVDF aerogel of claim 10.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811310277.9A CN109320882B (en) | 2018-11-05 | 2018-11-05 | Silica-modified PVDF aerogel, preparation method and aerogel product comprising same |
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| CN201811310277.9A CN109320882B (en) | 2018-11-05 | 2018-11-05 | Silica-modified PVDF aerogel, preparation method and aerogel product comprising same |
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| CN105609741A (en) * | 2016-03-04 | 2016-05-25 | 湘潭大学 | Preparation of silicon dioxide/titanium dioxide composite aerogel for lithium battery negative electrode material |
| CN105802220A (en) * | 2016-04-06 | 2016-07-27 | 同济大学 | Preparation method of polyimide/silicon dioxide aerogel powder composite aerogel material |
| CN106189066A (en) * | 2016-07-04 | 2016-12-07 | 中国科学技术大学 | A kind of phenolic resin/silicon dioxide composite aerogel material and preparation method thereof |
| CN106731900A (en) * | 2017-01-12 | 2017-05-31 | 常州大学 | In-situ sol-gel high-strength polyvinylidene fluoride milipore filter and preparation method |
| CN107915467A (en) * | 2017-10-25 | 2018-04-17 | 成都圻坊生物科技有限公司 | A kind of preparation method of construction wall aerosil thermal insulation material |
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| CN105609741A (en) * | 2016-03-04 | 2016-05-25 | 湘潭大学 | Preparation of silicon dioxide/titanium dioxide composite aerogel for lithium battery negative electrode material |
| CN105802220A (en) * | 2016-04-06 | 2016-07-27 | 同济大学 | Preparation method of polyimide/silicon dioxide aerogel powder composite aerogel material |
| CN106189066A (en) * | 2016-07-04 | 2016-12-07 | 中国科学技术大学 | A kind of phenolic resin/silicon dioxide composite aerogel material and preparation method thereof |
| CN106731900A (en) * | 2017-01-12 | 2017-05-31 | 常州大学 | In-situ sol-gel high-strength polyvinylidene fluoride milipore filter and preparation method |
| CN107915467A (en) * | 2017-10-25 | 2018-04-17 | 成都圻坊生物科技有限公司 | A kind of preparation method of construction wall aerosil thermal insulation material |
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