CN116102773B - Method for preparing organic-silicon dioxide composite aerogel by click reaction - Google Patents
Method for preparing organic-silicon dioxide composite aerogel by click reaction Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 31
- 238000012650 click reaction Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 238000011417 postcuring Methods 0.000 claims abstract description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011240 wet gel Substances 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 238000009413 insulation Methods 0.000 abstract description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical group CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 125000000304 alkynyl group Chemical group 0.000 abstract 1
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 4
- -1 polysiloxane Polymers 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
-
- 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
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention belongs to the technical field of aerogel material preparation, and particularly relates to a method for preparing organic-silicon dioxide composite aerogel by click reaction. In a low boiling point solvent, the precursor solution is prepared by click reaction of sulfhydryl groups of silicon aryne resin PSA containing terminal alkynyl and mercaptopropyl triethoxysilane MPTES. The precursor solution is subjected to sol-gel, aging, freeze drying and post curing to obtain the silicon-containing aryne resin modified SiO 2 Porous material of aerogel framework. The aerogel prepared by the method has low density, low thermal conductivity and excellent heat resistance, is simple in process, does not need a catalytic gel and solvent replacement process, and has higher compressive strength. The prepared aerogel material can be applied to ultra-light heat insulation in the high-temperature field.
Description
Technical Field
The invention belongs to the technical field of aerogel material preparation, and particularly relates to a method for preparing organic-silicon dioxide composite aerogel by click reaction
Background
SiO 2 Aerogel is a kind ofHighly crosslinked porous materials, having low density, high porosity and low thermal conductance, have a complex three-dimensional structure that can effectively expand the heat transfer path, thereby providing good thermal insulation properties. SiO (SiO) 2 Aerogel is made of SiO 2 Nano particles are piled up to form a 'pearl chain' structure, and a 'neck' region is extremely easy to generate brittle fracture of a gel skeleton under the action of external force, so that SiO 2 The aerogel has low mechanical strength and large brittleness. At present, researchers are about SiO 2 The technical route of mechanical modification of aerogel mainly comprises polymer reinforcement, fiber and other composite reinforcement. The polymer reinforcement is an organic polymer and SiO 2 The skeletons are connected by covalent bonds, the polymer coats the aerogel skeletons and strengthens and toughens the skeletons to form the organic-inorganic composite polymer reinforced SiO 2 Aerogel framework structure. CN 111924850a utilizes SiO 2 The wet gel skeleton surface residual plenty of-OH, polyisocyanate as cross-linking agent to strengthen, the sample has high reversible compression deformation. CN109796018A uses alkoxysilane containing vinyl or allyl as a precursor, and a double-crosslinked nano porous structure composed of polysiloxane and hydrocarbon chain, so as to prepare polyethylene polysiloxane aerogel. The samples have excellent compressibility and elasticity and good bending properties, but the preparation process requires 2-4 days of solvent replacement, high-cost supercritical drying or 1-2 days of normal pressure drying. Nguyen et al uses 3-aminopropyl triethoxysilane APTES as a silicon source, and the amino-containing wet gel and diisocyanate undergo a crosslinking reaction to obtain polyurea enhanced SiO 2 Aerogels (ACS Applied Materials and Interfaces,2010,2 (5): 1430-1443.). Similarly, styrene, epoxy-reinforced SiO can be obtained 2 Aerogel armatures (Chemistry ofMaterials,2008,20 (15): 5035-5046.). The polymer can obviously strengthen SiO 2 The mechanical properties of aerogel, but the high temperature stability of polymer with crosslinking enhancement effect is poor, and the silane hydrolysis gel process usually needs acid-base catalysis, and in addition, the long-time solvent replacement process and supercritical drying make the process lengthy and increase the preparation cost.
Disclosure of Invention
The invention aims to provide a method for preparing organic-silicon dioxide composite aerogel by click reaction. The aerogel has low density, low thermal conductivity and excellent heat resistance, is simple in process, does not need a catalytic gel and solvent replacement process, and has better compressive strength.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for preparing organic-silicon dioxide composite aerogel by click reaction comprises the following steps:
(1) Precursor solution preparation: dissolving azobisisobutyronitrile AIBN and silicon-containing aryne resin PSA in a low-boiling point solvent, then dropwise adding mercaptopropyl triethoxysilane MPTES, and carrying out click reaction for 4 hours under the conditions of no water and no oxygen and 105 ℃ to obtain a precursor solution;
(2) Preparation of aerogel: and (3) preserving heat of the precursor solution in the step (1) for 12 hours at 45 ℃, adding deionized water, heating to 145 ℃ and refluxing for 30 minutes, transferring to a beaker, aging to obtain wet gel, and freezing, freeze-drying and post-curing the wet gel by liquid nitrogen to obtain the aerogel material.
In the present invention, the PSA has the structural formula:
R 1 ＝H，CH 3
R 2 ＝H,CH 3 ，CH＝CH 2 ，Ph
n＝6～10
in the invention, the mass ratio of the PSA to the MPTES in the step (1) is (0.8-1.5): 1; the addition amount of the dioxane is 9wt% of MPTES concentration, and the mass fraction of AIBN is 3 wt%.
In the present invention, the low boiling point solvent in the step (1) is preferably dioxane, cyclohexane, 1, 2-dichloroethane.
In the invention, deionized water and alkoxy of MPTES are added in the step (2) in an equimolar manner.
In the invention, the step (2) is aged for 2 hours at room temperature or is aged for 2 hours at 60 ℃ in a heat preservation way;
in the present invention, the freezing of liquid nitrogen in step (2) subjects the wet gel to conditions sufficient to freeze the solvent to form frozen material.
In the invention, the pressure of the freeze drying in the step (2) is 10-30 Pa, the temperature is-50 ℃ to-45 ℃ and the time is 12-18 h.
In the present invention, the post-curing procedure in step (2) is 150 ℃/2h, 170 ℃/2h, 210 ℃/2h and 250 ℃/4h.
The invention also provides the organic-silicon dioxide composite aerogel prepared by the method for preparing the organic-silicon dioxide composite aerogel through the click reaction.
The beneficial effects obtained by the invention are as follows:
compared with the prior art, the invention is used for reinforcing SiO 2 The polymer of the aerogel framework is PSA resin with excellent thermal performance and is used for improving the high-temperature stability of the composite aerogel polymer matrix. PSA on SiO 2 And the surface of the aerogel framework is subjected to sulfydryl-alkyne click reaction to form the PSA coated aerogel framework for reinforcing and toughening, so that the mechanical property is improved. The precursor solution is subjected to high temperature and high temperature reflux without acid-base catalysis gel. In addition, gel is obtained in a low boiling point solvent, and aerogel materials are obtained by direct freeze drying. The process is simple, long-time solvent replacement is avoided, and a large amount of replacement solvent is not used to realize green production. The prepared aerogel material can be applied to ultra-light heat insulation in the high-temperature field.
Drawings
FIG. 1 is an organic-silica composite aerogel material prepared in example 1.
FIG. 2 is a scanning electron microscope image of the organic-silica composite aerogel material prepared in example 1.
FIG. 3 is a graph showing the thermal weight loss curve of the organic-silica composite aerogel material prepared in example 4.
FIG. 4 is a graph showing the compression curve of the organic-silica composite aerogel material prepared in example 4.
Detailed Description
The following describes the embodiment of the present invention in further detail with reference to example 1
The organic-silicon dioxide composite aerogel is prepared according to the following method:
(1) Preparing a precursor solution: 0.20g of AIBN and 4.80g of PSA are dissolved in 55.87g of dioxane at room temperature with stirring, and then 6.00g of MPTES are added dropwise. And carrying out back-flow click reaction for 4 hours at 105 ℃ under the conditions of no water and no oxygen to obtain a precursor solution.
(2) Preparation of aerogel materials: the precursor solution is kept at 45 ℃ for 12 hours, 1.36g of deionized water is added, the temperature is raised to 145 ℃ for refluxing for 30 minutes, and the mixture is transferred into a beaker for ageing for 2 hours at room temperature to obtain wet gel. The wet gel is frozen by liquid nitrogen for 20min and then freeze-dried, the pressure is 10 Pa to 30Pa, the temperature is minus 50 ℃ to minus 45 ℃ and the time is 18h. Finally, post-curing is carried out in a forced air drying oven with curing procedures of 150 ℃/2h, 170 ℃/2h, 190 ℃/2h and 210 ℃/4h. Obtaining the organic-silicon dioxide composite aerogel.
The organic-silica composite aerogel material prepared in example 1 is shown in fig. 1.
A scanning electron microscope image of the organic-silica composite aerogel material prepared in example 1 is shown in fig. 2.
Example 2
The organic-silicon dioxide composite aerogel is prepared according to the following method:
in example 1, 4.80g of PSA and 55.87g of dioxane were used in place of 6.00g of PSA and 54.67g of dioxane. Other process steps were the same as in example 1.
Example 3
The organic-silicon dioxide composite aerogel is prepared according to the following method:
in example 1, 4.80g of PSA and 55.87g of dioxane were used in place of 7.50g of PSA and 53.17g of dioxane. Other process steps were the same as in example 1.
Example 4
The organic-silicon dioxide composite aerogel is prepared according to the following method:
in example 1, 4.80g of PSA and 55.87g of dioxane were used in place of 9.00g of PSA and 51.67g of dioxane. Other process steps were the same as in example 1.
Example 5
The organic-silicon dioxide composite aerogel is prepared according to the following method:
in example 1, the dioxane used was replaced by 1, 2-dichloroethane. Other process steps were the same as in example 1.
Example 6
The organic-silicon dioxide composite aerogel is prepared according to the following method:
in example 1, dioxane used was replaced by cyclohexane and room temperature aging was replaced by heat-preserving aging at 60 ℃. Other process steps were the same as in example 1.
Example 7
The organic-silicon dioxide composite aerogel is prepared according to the following method:
in example 4, the curing procedure used at 150 ℃/2h, 170 ℃/2h, 210 ℃/2h and 250 ℃/4h was replaced with 150 ℃/2h, 170 ℃/2h, 190 ℃/2h and 210 ℃/4h. Other process steps were the same as in example 1.
To determine the optimal conditions for the present invention, the aerogels of the above examples were tested for performance as follows:
1. determination of the ratio of PSA to MPTES in a precursor solution
Examples 1-4 explore the effect of PSA to MPTES ratio in precursor solution on aerogel properties. The test results are shown in tables 1-3 below.
TABLE 1 influence of the ratio of PSA to MPTES in precursor solution on aerogel thermal conductivity
TABLE 2 influence of the ratio of PSA to MPTES in precursor solution on aerogel Heat resistance
| m PSA :m MPTES | T d5 (℃) | Y r800 (℃) |
| 0.8:1 | 419.3 | 73.9 |
| 1:1 | 430.4 | 76.1 |
| 1.2:1 | 474.4 | 81.2 |
| 1.5:1 | 492.9 | 83.7 |
TABLE 3 influence of the ratio of PSA to MPTES in precursor solution on aerogel mechanical Properties
As can be seen from tables 1-3, as the PSA content in the precursor solution increases, the aerogel density increases and the thermal conductivity increases, but the PSA aerogel thermal stability and compressive strength increases. For insulating materials, lower thermal conductivity means better insulating properties. Preferred precursor solutions of the invention are m PSA :m MPTES The ratio was 0.8:1.
2. Determination of low boiling point solvents in precursor solutions
Examples 1 and 5-6 explore the effect of low boiling solvents in precursor solutions on aerogel properties.
TABLE 4 influence of low boiling solvents in precursor solutions on gel
| Low boiling point solvent | Melting point (. Degree. C.) | Boiling point (. Degree. C.) | Gel conditions |
| Dioxahexacyclic ring | 6.5 | 101.1 | RT, ageing for 2h |
| 1, 2-dichloroethane | -35.3 | 83.5 | RT, ageing for 2h |
| Cyclohexane | 11.8 | 80.7 | Aging at 60℃for 2h |
As can be seen from Table 4, dioxane, 1, 2-dichloroethane and cyclohexane as low boiling point solvents can be used directly for freeze drying, wherein cyclohexane is difficult to gel and requires a temperature of 60 ℃; the melting point of 1, 2-dichloroethane is lower and the time for forming wet gel into frozen material by liquid nitrogen freezing is longer. The preferred low boiling solvent for the present invention is dioxane.
3. Determination of post-cure procedure
Examples 1 and 7 explore the effect of post-cure procedures on aerogel properties.
TABLE 5 influence of curing procedure on aerogel thermal properties
| Curing procedure | T d5 (℃) | Y r800 (℃) |
| Example 1 | 492.9 | 83.7 |
| Example 7 | 482.2 | 82.1 |
Based on the DSC results, two curing procedures for the aerogel were analyzed and determined. As can be seen from Table 5, the preferred curing procedures of the present invention are 150 ℃/2h, 170 ℃/2h, 210 ℃/2h and 250 ℃/4h.
Claims (8)
1. A method for preparing organic-silicon dioxide composite aerogel by click reaction, which is characterized by comprising the following steps:
(1) Precursor solution preparation: dissolving azobisisobutyronitrile AIBN and PSA in a low boiling point solvent, then dropwise adding MPTES, and carrying out click reaction for 4 hours at 105 ℃ without water and oxygen to obtain a precursor solution; the mass ratio of the PSA to the MPTES is (0.8-1.5): 1; the addition amount of the low boiling point solvent is 9wt% of MPTES concentration, and the mass fraction of AIBN is 3 wt%;
(2) Preparation of aerogel: keeping the temperature of the precursor solution in the step (1) at 45 ℃ for 12 hours, adding deionized water, heating to 145 ℃ and refluxing for 30 minutes, transferring to a beaker, and aging for 2 hours to obtain wet gel; freezing the wet gel by liquid nitrogen, freeze-drying and post-curing to obtain an aerogel material;
the structural formula of the PSA is as follows:
2. the method for preparing organic-silica composite aerogel according to claim 1, wherein the melting point of the low boiling point solvent in the step (1) is higher than-50 ℃; the boiling point is 50-150 ℃.
3. The method for preparing organic-silica composite aerogel according to claim 1, wherein the low boiling point solvent in the step (1) is dioxane, cyclohexane, 1, 2-dichloroethane.
4. The method for preparing organic/silica composite aerogel according to claim 1, wherein deionized water and alkoxy groups of MPTES are added in equimolar manner in the step (2).
5. The method for preparing organic-silicon dioxide composite aerogel according to claim 1, wherein the aging in the step (2) is room temperature aging or 60 ℃ heat preservation aging.
6. The method for preparing organic-silicon dioxide composite aerogel according to claim 1, wherein the pressure of freeze drying in the step (2) is 10-30 Pa, the temperature is-50 ℃ to-45 ℃ and the time is 12-18 h.
7. The method for preparing organic-silica composite aerogel according to claim 1, wherein the post-curing procedure in the step (2) is 150 ℃/2h, 170 ℃/2h, 210 ℃/2h and 250 ℃/4h.
8. An organic-silica composite aerogel prepared by the method of preparing an organic-silica composite aerogel according to any one of claims 1 to 6.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0464289A2 (en) * | 1990-07-02 | 1992-01-08 | Nalco Chemical Company | Preparation of silica sols |
| CN101838380A (en) * | 2009-03-19 | 2010-09-22 | 华东理工大学 | Propargyl ether modified silicon-containing aryne resin |
| CN104640899A (en) * | 2012-09-18 | 2015-05-20 | 巴斯夫欧洲公司 | Polymers comprising a polyurethane backbone endcapped with reactive (meth)acrylic terminating groups and their use as adhesives |
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2022
- 2022-12-01 CN CN202211530578.9A patent/CN116102773B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0464289A2 (en) * | 1990-07-02 | 1992-01-08 | Nalco Chemical Company | Preparation of silica sols |
| CN101838380A (en) * | 2009-03-19 | 2010-09-22 | 华东理工大学 | Propargyl ether modified silicon-containing aryne resin |
| CN104640899A (en) * | 2012-09-18 | 2015-05-20 | 巴斯夫欧洲公司 | Polymers comprising a polyurethane backbone endcapped with reactive (meth)acrylic terminating groups and their use as adhesives |
Non-Patent Citations (2)
| Title |
|---|
| "Synthesis and characterization of SAR/SiO2 hybrid materials with high thermal stability";Jian Zhang et al.;《Advanced Materials Research》;20110221;第571-575页 * |
| "Thermally Insulating SiO2/PSA Composite Aerogels with Heat Resistance and Mechanical Properties via the Thiol−Yne Click Reaction";Chuanqing Zhao et al.;《Langmuir》;20230129;第9468−9475页 * |
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