CN115253937B - SiO preparation method based on water glass2Method for polymerizing ionic liquid aerogel - Google Patents
SiO preparation method based on water glass2Method for polymerizing ionic liquid aerogel Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 68
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title description 2
- 230000000379 polymerizing effect Effects 0.000 title 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 45
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 32
- -1 (2-methoxyethyl) -N-vinyl ethylamine chloride salt Chemical compound 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 30
- 238000012986 modification Methods 0.000 claims description 29
- 230000004048 modification Effects 0.000 claims description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 29
- 235000019441 ethanol Nutrition 0.000 claims description 18
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000011240 wet gel Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000000499 gel Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- IBZKBSXREAQDTO-UHFFFAOYSA-N 2-methoxy-n-(2-methoxyethyl)ethanamine Chemical compound COCCNCCOC IBZKBSXREAQDTO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 238000000352 supercritical drying Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 18
- 238000011056 performance test Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004965 Silica aerogel Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- GPUZITRZAZLGKZ-UHFFFAOYSA-N 1-hexyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCC[NH+]1CN(C)C=C1 GPUZITRZAZLGKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000012835 hanging drop method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a method for preparing SiO 2/polyion liquid aerogel based on water glass, and belongs to the technical field of inorganic materials. According to the invention, the ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt is prepared, and then the ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt and water glass are utilized to form the double-network aerogel, so that the problems of low porosity, poor high temperature resistance and poor mechanical property of the aerogel are solved. In addition, the method can reduce the use of organic solvents, the adopted water glass is low in price, the traditional organic silicon alkoxide can be replaced to be used as a silicon source of the silicon dioxide aerogel, and the safe and simple normal-pressure drying process is used to replace the traditional supercritical drying process, so that the production cost and the dangers under the supercritical drying condition are greatly reduced.
Description
Technical Field
The invention relates to a method for preparing SiO 2/polyion liquid aerogel based on water glass, and belongs to the technical field of inorganic materials.
Background
The unique nano porous three-dimensional network structure of the SiO 2 aerogel has the advantages of low density (as low as 3kg/m 3), high porosity (80% -99.8%), high specific surface area (200-1000 m 2/g), ultralow heat conductivity (as low as 0.013W/(m.K), high temperature resistance (1400 ℃)), excellent heat insulation performance, good fireproof performance, A-grade nonflammable material, green and harmless, and is the aerogel material most studied in the field of heat insulation and heat preservation at present. However, the pure SiO 2 aerogel has the defects of fragile network skeleton, easy collapse, low mechanical strength, poor toughness and the like, and limits the application of the pure SiO 2 aerogel in the field of heat preservation and heat insulation.
At present, researchers compound SiO 2 aerogel with some fibers, polymers and the like to prepare reinforced modified SiO 2 aerogel composite materials; however, although the fiber material can improve the mechanical property of the SiO 2 aerogel, the two are difficult to form microscopically uniform composite, the combination is not tight, and the practical application of the SiO 2 aerogel is limited.
Some researchers also form chemical bonds between the hydroxyl groups of the SiO 2 aerogel and the polymer to enhance the interconnection between SiO 2 gel particles, and endow the gel skeleton with certain flexibility, so that the mechanical properties of the SiO 2 aerogel are effectively improved. However, many polymers used have certain toxicity and are difficult to dissolve in water, and a large amount of organic solvents are needed, so that the environmental friendliness is further reduced, and the complexity and toxicity of the process for preparing the SiO 2 aerogel are increased. Moreover, the introduction of the polymer generally results in an increase in the bulk density of the aerogel and a decrease in the resistance to high temperatures, which have a certain effect on the properties of the aerogel. In addition, the commonly used silicon sources, such as tetraethyl orthosilicate (TEOS) and methyl orthosilicate (TMOS), are expensive and toxic, have high production cost and cause environmental pollution.
Still other researchers use ionic liquids and SiO 2 aerogel to combine to improve the performance of SiO 2 aerogel, but the usual ionic liquid monomer is imidazole ionic liquid, and the imidazole ring with larger volume can cause the void blockage of the network, so that aerogel with high porosity cannot be formed.
Disclosure of Invention
In order to solve the problems, the invention firstly prepares the Ionic Liquid (IL) N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt, and then utilizes the ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt and water glass to form the double-network aerogel, so as to solve the problems of low porosity, poor high temperature resistance and poor mechanical property of the aerogel. In addition, the method can reduce the use of organic solvents, the adopted water glass is low in price, the traditional organic silicon alkoxide can be replaced to be used as a silicon source of the silicon dioxide aerogel, and the safe and simple normal-pressure drying process is used to replace the traditional supercritical drying process, so that the production cost and the dangers under the supercritical drying condition are greatly reduced.
The first object of the invention is to provide a method for preparing SiO 2/polyionic liquid aerogel based on water glass, which comprises the following steps:
(1) Di (2-methoxyethyl) amine and 1, 2-dichloroethane are mixed according to a molar ratio of 1:2, mixing, and reacting for 12 hours at 80 ℃ by using NaCO 3 as a catalyst to obtain a substance (1) and a byproduct solution; then the substance (1) and the byproduct solution are mixed according to the mol ratio of the substance (1) to NaH of 1:2, mixing, reacting for 12 hours at 80 ℃ to obtain N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt and byproduct solution, and rotating to obtain unpurified ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt;
Wherein the structural formula of the substance (1) is shown as the following formula I:
(2) Adding water into water glass for dilution to obtain water glass diluent; adding ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt into the water glass diluent, and uniformly mixing to obtain a mixture of water glass and the ionic liquid; adding 2,2' -azobisisobutyronidazole hydrochloride into the mixture of water glass and ionic liquid, and continuously and uniformly mixing to obtain a mixed solution; purging the mixed solution with nitrogen, adding an acid solution to adjust the pH to 7-9, and then irradiating with UV light to form wet gel;
(3) Aging the wet gel at 25-50deg.C for 10-48 hr to obtain aged wet gel;
(4) Performing solvent replacement on the aged wet gel by using absolute ethyl alcohol to obtain alcohol gel;
(5) Adding a surface modification liquid into the alcohol gel for hydrophobic modification; wherein the surface modification liquid is a mixed solution of methyltrimethoxysilane, n-hexane and ethanol;
(6) And after modification, cleaning and drying to obtain the SiO 2/polyion liquid aerogel.
In one embodiment of the invention, the amount of the catalyst NaCO 3 used in step (1) is 1% of the sum of the masses of the di (2-methoxyethyl) amine and 1, 2-dichloroethane.
In one embodiment of the present invention, the ionic liquid N, N-bis (2-methoxyethyl) -N-vinylamine chloride salt described in step (1) is synthesized as follows:
in one embodiment of the invention, the water glass in the step (2) is industrial water glass (pure sodium silicate), and the modulus of the water glass is 2.2-3.5.
In one embodiment of the present invention, the mass ratio of water glass to water in the water glass diluent in the step (2) is 1:10.
In one embodiment of the invention, the mass ratio of the water glass and the ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt in the step (2) is 12-25:1.
In one embodiment of the present invention, the molar ratio of the water glass and 2,2' -azobisisobutyrimidine hydrochloride of step (2) is 40-60:1.
In one embodiment of the invention, the acid solution in the step (2) comprises one or more of nitric acid solution, hydrochloric acid solution, oxalic acid solution and sulfuric acid solution, and the concentration of the acid solution is 0.5-3mol/L.
In one embodiment of the invention, the wavelength of the UV light in the step (2) is 350-400nm, the light intensity is 4mW/cm, and the irradiation is performed for 12 hours.
In one embodiment of the invention, the temperature of the replacement in the step (4) is 35-60 ℃, the number of times of replacement is 2-6, and the total time of replacement is 12-48 hours.
In one embodiment of the present invention, the volume ratio of methyltrimethoxysilane, n-hexane, and ethanol in the surface modification solution in step (5) is 1:0.5-1:4-10.
In one embodiment of the present invention, the hydrophobic modification described in step (5) is a modification at 30-50℃for 10-36h.
In one embodiment of the present invention, the hydrophobic modification described in step (5) may be performed 3 to 5 times.
In one embodiment of the invention, the hydrophobic modification in the step (5) is to add methyltrimethoxysilane, n-hexane and ethanol in a volume ratio of 1:0.88:9.1, carrying out first modification for 3 hours at the temperature of 30-50 ℃, and then adding methyltrimethoxysilane, n-hexane and ethanol in a volume ratio of 1:0.88:6.4, carrying out second modification for 6 hours at the temperature of 30-50 ℃, and finally adding methyltrimethoxysilane, n-hexane and ethanol in a volume ratio of 1:0.88:4.7, and carrying out the third modification for 9h at the temperature of 30-50 ℃.
In one embodiment of the present invention, the washing of step (6) is performed with n-hexane to remove unreacted methyltrimethoxysilane.
In one embodiment of the present invention, the drying in step (6) is performed in an oven under normal pressure, specifically, drying is performed at 50 ℃ for 3-6 hours, then at 80 ℃ for 4-8 hours, and finally at 130 ℃ for 2-3 hours.
The second purpose of the invention is SiO 2/polyionic liquid aerogel prepared by the method.
The third purpose of the invention is to apply the SiO 2/polyionic liquid aerogel in the field of heat insulation.
The invention has the beneficial effects that:
(1) According to the invention, the low-cost water glass is used for replacing the traditional organic silicon alkoxide to prepare the aerogel as a silicon source, and the cation exchange resin is not used for carrying out cation exchange on the water glass to remove sodium ions, so that the production cost is greatly reduced.
(2) The ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt and SiO 2 adopted by the invention are respectively continuous phases, and are compounded to form an interpenetrating double network, so that the mechanical property of the silica aerogel is improved, and meanwhile, the silica aerogel has good thermal stability.
(3) The SiO 2/polyionic liquid aerogel prepared by the method has the excellent performances of high strength, high porosity, high specific surface area and low heat conductivity coefficient, and expands the application field of the aerogel.
(4) The invention adopts a safe and simple normal pressure drying process to replace the traditional supercritical drying process, thereby greatly reducing the process requirements and avoiding the dangers under the supercritical drying condition.
Drawings
FIG. 1 is a physical diagram of SiO 2/polyionic liquid aerogel prepared in example 1.
FIG. 2 is a graph showing the hydrophobicity test of SiO 2/polyionic liquid aerogel prepared in example 1.
FIG. 3 is a thermogravimetric analysis of SiO 2/polyionic liquid aerogel prepared in example 1.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
1. Contact angle test:
The hydrophobic properties of the aerogel samples were characterized by water contact angle (θ) using germany DATAPHYSICS OCA, 20, and the contact angle of the aerogel samples with water was measured by the hanging drop method with a drop size of 5 μl.
2. Testing of density:
Adopting tap density test, weighing mass m 1 of a dry small measuring cylinder (with the specification of 5 mL), filling a certain volume of silicon dioxide aerogel powder, under tap 500, reading the volume V of the aerogel powder in the small measuring cylinder, weighing mass m 2 of the small measuring cylinder and aerogel, and calculating to obtain the tap density of the powder aerogel by using a formula (1);
pm＝(m2-m1)/V (1)
Wherein: m 1 is the mass of the measuring cylinder, g; m 2 is the mass, g, of the graduated cylinder containing the aerogel sample; v is the sample volume, cm, read through the cartridge.
3. Testing of specific surface area:
Samples were degassed at 150 ℃ for 3 hours prior to testing as determined by the N2 adsorption and desorption test at 77K using us Micromeritics ASAP 2460. The specific surface area of SiO2 aerogel was analyzed by the BET (Brunauer-Emmett-Twller) method, and the pore size distribution of the aerogel was calculated from the desorption branch of the adsorption isotherm using the BJH (Barrettr-Joynerr-Halenda) model.
4. Porosity test:
the porosity P can be calculated as equation (2):
P＝(1-pm/pA)x100％ (2)
wherein p A is the density of the theoretical porous silica, g/cm 3; here, 2.2g/cm 3;pm was taken as tap density. G/cm 3.
5. Testing of average pore size:
And obtaining the pore size distribution and average pore size data through BJH calculation.
6. Testing of compressive Strength:
The mechanical properties of the aerogel samples were tested using a universal tester according to the GB-T1448-2005 standard.
7. Testing of thermal conductivity:
the thermal conductivity of the samples was measured with the Hot Disk TPS 2500S, with reference to International Standard ISO 22007-2.
Example 1
The preparation method of the ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt comprises the following steps:
Di (2-methoxyethyl) amine and 1, 2-dichloroethane are mixed according to a molar ratio of 1:2, adding a catalyst NaCO 3 (the dosage is 1 percent of the sum of the mass of the di (2-methoxyethyl) amine and the mass of the 1, 2-dichloroethane), and reacting at 80 ℃ for 12 hours to obtain a substance (1) and a byproduct solution; then the substance (1) and the byproduct solution are mixed according to the mol ratio of the substance (1) to NaH of 1:2, mixing, reacting for 12 hours at 80 ℃ to obtain N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt and byproduct solution, and rotating to obtain unpurified ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt;
The specific synthetic route is as follows:
Example 2
A method for preparing SiO 2/polyionic liquid aerogel based on water glass comprises the following steps:
(1) According to the volume ratio of the water glass to the water of 1:10, adding water into water glass with the modulus of 2.35 for dilution to obtain water glass diluent; then according to the mass ratio of the water glass to the ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt of 12.39:1, adding ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt into water glass diluent, and uniformly mixing to obtain a mixture of water glass and the ionic liquid; adding 2,2 '-azobisisobutylaminine hydrochloride into a mixture of water glass and ionic liquid according to the mol ratio of the water glass to the 2,2' -azobisisobutylaminine hydrochloride being 40:1, and continuously and uniformly mixing to obtain a mixed solution; the mixed solution is purged by nitrogen, 0.5mol/L nitric acid solution is added to adjust the pH value to 7, and then UV light (the wavelength is 350-400nm and the light intensity is 4 mW/cm) is adopted for irradiation for 12 hours, so that wet gel is formed;
(2) Aging the wet gel at 25 ℃ for 24 hours to obtain the aged wet gel;
(3) Replacing the aged wet gel with absolute ethyl alcohol under the water bath condition of 45 ℃ for 4 times, wherein the total replacement time is 12 hours, so as to obtain the alcogel;
(4) Under the water bath condition of the alcohol gel at 40 ℃, methyl trimethoxy silane, n-hexane and ethanol are firstly added in the volume ratio of 1:0.88:9.1, carrying out first modification for 3 hours at 40 ℃; then methyl trimethoxy silane, n-hexane and ethanol are added according to the volume ratio of 1:0.88:6.4, carrying out secondary modification on the surface modification liquid at 40 ℃ for 6 hours; finally, methyl trimethoxy silane, n-hexane and ethanol are added according to the volume ratio of 1:0.88:4.7, carrying out third modification for 9h at 40 ℃;
(5) After the modification is finished, the modified gel is washed by normal hexane to remove unreacted methyltrimethoxysilane; and then drying in an oven under normal pressure, firstly drying at 50 ℃ for 6 hours, then drying at 80 ℃ for 8 hours, and finally drying at 130 ℃ for 2 hours to obtain the SiO 2/polyionic liquid aerogel.
The physical diagram of SiO 2/polyionic liquid aerogel is shown in figure 1, and the contact angle is shown in figure 2.
Example 3
The mass ratio of the water glass to the ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt in the step (1) of the example 2 is adjusted to be 16.52: 1. 20.65: 1. 24.78:1, otherwise in accordance with example 2, siO 2/polyionic liquid aerogel was obtained.
Performing performance test on the obtained SiO 2/polyionic liquid aerogel, wherein the test result is as follows:
TABLE 1
Example 4
The nitric acid solution in the step (1) of the example 2 is adjusted to be hydrochloric acid solution, oxalic acid solution and sulfuric acid solution, and other solutions are kept the same as the example 2, so that SiO 2/polyionic liquid aerogel is obtained.
Performing performance test on the obtained SiO 2/polyionic liquid aerogel, wherein the test result is as follows:
TABLE 2
Example 5
The pH was adjusted to 7, 8, 9 in step (1) of example 2, and the other was kept the same as in example 2 to obtain SiO 2/polyionic liquid aerogel.
Performing performance test on the obtained SiO 2/polyionic liquid aerogel, wherein the test result is as follows:
TABLE 3 Table 3
Example 6
The methyltrimethoxysilane in the step (4) of the example 2 is adjusted to be trimethylchlorosilane and hexamethyldisilazane, and other materials are kept the same as the example 2, so that SiO 2/polyion liquid aerogel is obtained.
Performing performance test on the obtained SiO 2/polyionic liquid aerogel, wherein the test result is as follows:
TABLE 4 Table 4
Example 7
The drying mode in the step (5) of the example 2 was adjusted to be freeze-drying (the wet gel was frozen at-70 ℃ C. For 12 hours and then dried under vacuum for 24 hours to prepare SiO2 aerogel.) and the other steps were kept the same as the example 2 to obtain SiO 2/polyionic liquid aerogel.
Performing performance test on the obtained SiO 2/polyionic liquid aerogel, wherein the test result is as follows:
TABLE 5
Comparative example 1
The ionic liquid N, N-bis (2-methoxyethyl) -N-vinylamine chloride salt in the step (1) of the example 2 is omitted, and other steps are consistent with the example 2, so that SiO 2/polyionic liquid aerogel is obtained.
Comparative example 2
The ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt in the step (1) of the example 2 was adjusted to be 1-hexyl-3 methylimidazole chloride salt, and the other steps were kept the same as the example 2 to obtain SiO 2/polyionic liquid aerogel.
Comparative example 3
Omitting 2,2' -azobisisobutyronimidine hydrochloride in step (1) of example 2, the other was identical to example 2 to obtain SiO 2/polyionic liquid aerogel.
Performing performance test on the obtained SiO 2/polyionic liquid aerogel, wherein the test result is as follows:
TABLE 6
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The method for preparing SiO 2/polyionic liquid aerogel based on water glass is characterized by comprising the following steps:
(1) Di (2-methoxyethyl) amine and 1, 2-dichloroethane are mixed according to a molar ratio of 1:2, mixing, and reacting for 12 hours at 80 ℃ by using NaCO 3 as a catalyst to obtain a substance (1) and a byproduct solution; then the substance (1) and the byproduct solution are mixed according to the mol ratio of the substance (1) to NaH of 1:2, mixing, reacting for 12 hours at 80 ℃ to obtain N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt and byproduct solution, and rotating to obtain unpurified ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt;
Wherein the structural formula of the substance (1) is shown as the following formula I:
(2) Adding water into water glass for dilution to obtain water glass diluent; adding ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt into the water glass diluent, and uniformly mixing to obtain a mixture of water glass and the ionic liquid; adding 2,2' -azobisisobutyronidazole hydrochloride into the mixture of water glass and ionic liquid, and continuously and uniformly mixing to obtain a mixed solution; purging the mixed solution with nitrogen, adding an acid solution to adjust the pH to 7-9, and then irradiating with UV light to form wet gel;
(3) Aging the wet gel at 25-50deg.C for 10-48 hr to obtain aged wet gel;
(4) Performing solvent replacement on the aged wet gel by using absolute ethyl alcohol to obtain alcohol gel;
(5) Adding a surface modification liquid into the alcohol gel for hydrophobic modification; wherein the surface modification liquid is a mixed solution of methyltrimethoxysilane, n-hexane and ethanol;
(6) And after modification, cleaning and drying to obtain the SiO 2/polyion liquid aerogel.
2. The method according to claim 1, wherein the mass ratio of the water glass and the ionic liquid N, N-bis (2-methoxyethyl) -N-vinyl ethylamine chloride salt in the step (2) is 12-25:1.
3. The method of claim 1, wherein the acid solution of step (2) comprises one or more of nitric acid solution, hydrochloric acid solution, oxalic acid solution, or sulfuric acid solution.
4. The method according to claim 1, wherein the molar ratio of water glass to 2,2' -azobisisobutyrimidine hydrochloride in step (2) is 40-60:1.
5. The method according to claim 1, wherein the volume ratio of methyltrimethoxysilane, n-hexane and ethanol in the surface modification solution in step (5) is 1:0.5-1:4-10.
6. The method of claim 1, wherein the hydrophobic modification in step (5) is a modification at 30-50 ℃ for 10-36 hours.
7. The method according to claim 1, wherein the drying in step (6) is performed in an oven at normal pressure, specifically at 50 ℃ for 3-6 hours, at 80 ℃ for 4-8 hours, and at 130 ℃ for 2-3 hours.
8. The method according to claim 1, wherein the hydrophobic modification in the step (5) is to add methyltrimethoxysilane, n-hexane and ethanol in a volume ratio of 1:0.88:9.1, carrying out first modification for 3 hours at the temperature of 30-50 ℃, and then adding methyltrimethoxysilane, n-hexane and ethanol in a volume ratio of 1:0.88:6.4, carrying out second modification for 6 hours at the temperature of 30-50 ℃, and finally adding methyltrimethoxysilane, n-hexane and ethanol in a volume ratio of 1:0.88:4.7, and carrying out the third modification for 9h at the temperature of 30-50 ℃.
9. The SiO 2/polyionic liquid aerogel prepared by the method of any one of claims 1-8.
10. The use of the SiO 2/polyionic liquid aerogel of claim 9 in the field of thermal insulation.
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| CN111392734A (en) * | 2020-04-23 | 2020-07-10 | 中南大学 | Block silicon dioxide aerogel with adjustable hydrophilicity and hydrophobicity and preparation method thereof |
| CN114276381A (en) * | 2021-12-30 | 2022-04-05 | 漳州卓施特建材有限公司 | Ionic liquid modifier for producing silicon dioxide aerogel and preparation method thereof |
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| CN101456569A (en) * | 2008-07-22 | 2009-06-17 | 绍兴纳诺气凝胶新材料研发中心有限公司 | Method for quick-speed preparing aerogel by hydro-thermal synthesis at low cost |
| CN109052415A (en) * | 2018-09-10 | 2018-12-21 | 西南科技大学 | Aerosil and preparation method thereof based on MTMS |
| CN111217373A (en) * | 2020-03-03 | 2020-06-02 | 中南大学 | Silica aerogel with customizable shape and rapid preparation method thereof |
| CN111392734A (en) * | 2020-04-23 | 2020-07-10 | 中南大学 | Block silicon dioxide aerogel with adjustable hydrophilicity and hydrophobicity and preparation method thereof |
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