CN116355272B - Preparation method of ethyl cellulose stable light heat insulation aerogel - Google Patents
Preparation method of ethyl cellulose stable light heat insulation aerogel Download PDFInfo
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- CN116355272B CN116355272B CN202310298536.5A CN202310298536A CN116355272B CN 116355272 B CN116355272 B CN 116355272B CN 202310298536 A CN202310298536 A CN 202310298536A CN 116355272 B CN116355272 B CN 116355272B
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- 239000004964 aerogel Substances 0.000 title claims abstract description 172
- 238000009413 insulation Methods 0.000 title claims abstract description 77
- 239000001856 Ethyl cellulose Substances 0.000 title claims abstract description 54
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229920001249 ethyl cellulose Polymers 0.000 title claims abstract description 54
- 235000019325 ethyl cellulose Nutrition 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 108
- 239000000463 material Substances 0.000 claims abstract description 95
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 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 abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 230000010355 oscillation Effects 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000011324 bead Substances 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims description 71
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 30
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 15
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 102
- 239000000047 product Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 22
- 239000004005 microsphere Substances 0.000 description 19
- 238000010586 diagram Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 241000245665 Taraxacum Species 0.000 description 5
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012774 insulation material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/14—Copolymers of styrene with unsaturated esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
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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
- C08K7/28—Glass
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Abstract
The invention discloses a preparation method of ethyl cellulose stable light heat insulation aerogel, which comprises the following steps: 1. mixing a polymerizable monomer and a cross-linking agent, adding ethyl cellulose, azodiisobutyronitrile and hollow glass beads, and then adding a water phase for high-speed oscillation; 2. introducing nitrogen into the gel emulsion, then placing the gel emulsion into an oil bath for polymerization, and then washing and drying the product at normal temperature in sequence; 3. and heating the aerogel block to obtain the light heat insulation aerogel material. According to the invention, the ethyl cellulose is used as a stabilizer, the continuous phase and the disperse phase are mixed in an oscillating way to obtain the gel emulsion with a large-range internal phase volume fraction, the thermal insulation aerogel material is obtained after polymerization and drying, the gel emulsion is connected with the polymer aerogel through the template effect, and the parameters such as the mechanical property, the density, the porosity, the heat conductivity coefficient and the like of the aerogel material are greatly regulated and controlled, so that the method is simple to operate, good in controllability, capable of being prepared in a large scale, and used in various fields such as aerospace, oil gas pipeline thermal insulation and the like.
Description
Technical Field
The invention belongs to the technical field of aerogel material preparation, and particularly relates to a preparation method of ethyl cellulose-stabilized light heat insulation aerogel.
Background
The heat insulating material has wide application and great application prospect in the fields of national defense, military industry, aerospace, petroleum, chemical industry, civil buildings and the like. The heat insulation material mainly plays roles of protection, energy conservation and emission reduction, and at present, china puts forward higher requirements on heat insulation systems and materials, and the heat insulation materials have lower heat conductivity and develop towards the directions of light weight, high efficiency, low heat conductivity, green preparation process and the like.
Aerogel is a solid material with a three-dimensional space network structure formed by aggregation of nano colloid particles or high molecular polymers, and has the excellent properties of ultra-light weight, high porosity, low thermal conductivity, low dielectric constant and the like. Has wide application prospect in the fields of chemistry, thermo-acoustics, optics, electricity and the like. In particular, in the field of high-performance heat insulation materials, aerogels are known as super heat insulation materials. Aerogel preparation technology has been developed, wherein the gel emulsion template method is paid attention to because of the advantages of simple preparation process, less solvent consumption, low energy consumption in the drying process, capability of doping nano fibers, nano microspheres and other mechanical reinforcing bodies. The unique gel emulsion method combines the advantages of emulsion and gel, so that the foam structure and gel state of the gel emulsion are ideal templates for preparing high-porosity aerogel. The gel emulsion is a two-phase system consisting of a continuous phase, a stabilizer and a disperse phase, however, the conventional surfactant and the conventional solid micro-nano particles are large in dosage and easy to phase inversion in the process of preparing the gel emulsion, and the time and labor are wasted in the synthesis of the small-molecule gelling agent. Experiments show that the gel emulsion is prepared by using ethyl cellulose as a stabilizer, the dosage of the gel emulsion is less than that of the non-traditional gel emulsion reported in the prior literature, and the internal phase volume ratio of the gel emulsion is far lower than 74 percent, which is rarely reported.
Based on the above, finding a mature commercial product as a gel emulsion stabilizer and preparing an aerogel material with an adjustable pore size structure, porosity and thermal conductivity is a great challenge to be solved in the field. Therefore, there is a need to develop a gel emulsion stabilizer with low dosage and high gel efficiency and a method for preparing light-weight heat insulation aerogel.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of ethyl cellulose-stabilized light heat insulation aerogel aiming at the defects of the prior art. According to the method, a gel emulsion template method is adopted, a polymerizable monomer and a cross-linking agent are mixed to obtain an oil phase, and ethyl cellulose, azodiisobutyronitrile and hollow glass beads are added for polymerization and heating, so that a network structure formed by a high molecular monomer is tightly compounded with the hollow glass beads, a light heat insulation aerogel material is obtained, the light heat insulation aerogel material has lower heat conductivity and density, excellent heat insulation performance is obtained, accurate regulation and control of porosity, pore size and heat conductivity can be realized, excellent mechanical properties are realized, the application range of aerogel products is widened, and heat insulation application under extreme humidity and high-heat environments is realized.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for preparing ethyl cellulose stabilized light insulating aerogel, which is characterized by comprising the following steps:
Step one, preparing a gel emulsion system: under the condition of room temperature, mixing a polymerizable monomer and a cross-linking agent to obtain an oil phase, adding ethyl cellulose, azodiisobutyronitrile and hollow glass beads into the oil phase, performing ultrasonic treatment, and adding a water phase to perform high-speed oscillation to obtain gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath for polymerization, and then washing and drying the product at normal temperature in sequence to obtain a porous polymer aerogel block material with ultra-low density;
Preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace for heating, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
The invention firstly mixes polymerizable monomer and cross-linking agent to be used as oil phase, provides stable gel skeleton structure after polymerization, adds non-water-soluble ethyl cellulose as gel emulsion stabilizer to the oil phase, plays a vital role in gel emulsion formation, reduces oil-water interfacial tension, stabilizes the whole system to form stable gel emulsion, simultaneously uses azo diisobutyronitrile as initiator of free radical polymerization, simultaneously adds hollow glass microsphere to improve mechanical strength and heat insulation performance, completely dissolves ethyl cellulose by ultrasound, then adds water phase with different volumes to perform high-speed oscillation, observes the obtained mixture to be highly viscous, presents jelly emulsion, reverses test tube after standing, and obtains gel emulsion by gel emulsion system polymerization, obtains porous polymer aerogel block material with light low heat conductivity coefficient, and then further promotes the close combination of hollow glass microsphere and three-dimensional skeleton structure while enabling the aerogel network structure to become more transparent by heating, thus obtaining light heat insulation aerogel.
The preparation method of the light heat insulation aerogel with stable ethylcellulose is characterized in that the polymerizable monomer in the first step is styrene, the cross-linking agent is divinylbenzene and ethylene glycol dimethacrylate, the mass fractions of the styrene, the divinylbenzene and the ethylene glycol dimethacrylate in the oil phase are 9.5-71.4%, the mass of the ethylcellulose is 1-2% of the volume of the oil phase, the mass of the azobisisobutyronitrile is 1-2% of the volume of the oil phase, the mass of the hollow glass microsphere is 1-3% of the volume of the oil phase, wherein the mass unit is mg, and the volume unit is mu L. According to the invention, by controlling the mass fraction of styrene, divinylbenzene and ethylene glycol dimethacrylate in an oil phase and matching with water-insoluble ethyl cellulose as a gel emulsion stabilizer, a proper polymerizable monomer and the optimal proportion of the polymerizable monomer and a cross-linking agent are obtained, the content of the stabilizer is reduced from 5-20% of the commonly reported dosage to 1-2% by optimizing the content of the stabilizer, so that high-efficiency stable gel emulsion is formed, the subsequent polymerization reaction is initiated by controlling the mass of azodiisobutyronitrile, the number of hollow glass microspheres in the light heat-insulating aerogel is controlled by controlling the mass of the hollow glass microspheres, and the light weight and heat-insulating effect of the light heat-insulating aerogel are ensured.
The preparation method of the ethyl cellulose stable light heat insulation aerogel is characterized in that the volume ratio of the oil phase to the water phase in the first step is 210:500-4000, and the water phase is distilled water. The internal phase volume fraction of the traditional gel emulsion is required to be more than 74 percent to form the gel emulsion, the internal phase volume fraction is as low as 70 percent, the stable gel emulsion can be formed, the water content of the gel emulsion can be regulated and controlled in a large range from 70 percent to 95 percent, the application range of the gel emulsion is widened by breaking through the internal phase volume, the water content plays a decisive role in the density and the porosity of the porous aerogel material by initiating the continuous phase to polymerize, and the density of the porous aerogel material can be effectively reduced by increasing the water content because the water does not participate in polymerization, the porosity of the aerogel is increased, and the heat conductivity coefficient of the aerogel is reduced.
The preparation method of the ethyl cellulose stable light heat insulation aerogel is characterized in that the water phase adding process in the first step is as follows: the sonicated product was placed in a homogenizer and then the aqueous phase was added dropwise. According to the invention, the oil phase is wrapped with more water phase as much as possible by dropwise adding the water phase.
The preparation method of the ethyl cellulose stable light heat insulation aerogel is characterized in that the polymerization process in the second step is as follows: prepolymerizing for 4-6 h at 35-45 ℃, and then raising the temperature to 60-85 ℃ for further polymerization for 10-20 h. The invention realizes low-temperature prepolymerization and high-temperature polymerization by gradient temperature control.
The preparation method of the ethyl cellulose stable light heat insulation aerogel is characterized in that the density of the ultra-low density porous polymer aerogel block in the second step is not more than 0.04g/cm -3, and the porosity is not less than 95%.
The preparation method of the ethyl cellulose stable light heat insulation aerogel is characterized in that the heating process in the third step is as follows: heating to 90-110 ℃ at a heating rate of 1-3 ℃/min, and then preserving heat for 1-2 h. According to the invention, by controlling the heating parameters, the aerogel network structure becomes more transparent, and the close combination of the hollow glass beads and the three-dimensional framework structure is further promoted, so that the light heat insulation aerogel is obtained.
The preparation method of the ethyl cellulose stable light heat insulation aerogel is characterized in that the density of the light heat insulation aerogel material in the third step is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K). The light heat insulation aerogel material prepared by the invention has the characteristics of low density, namely light weight, and low heat conductivity coefficient.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, by a gel emulsion template method, a polymerizable monomer and a cross-linking agent are mixed to obtain an oil phase, and ethyl cellulose, azodiisobutyronitrile and hollow glass beads are added for polymerization and heating, so that a network structure formed by a high molecular monomer is tightly compounded with the hollow glass beads, a light heat insulation aerogel material is obtained, the light heat insulation aerogel material has lower heat conductivity and density, excellent heat insulation performance is obtained, and accurate regulation and control of porosity, pore size and heat conductivity can be realized, meanwhile, excellent mechanical properties are realized, the application range of aerogel products is widened, and heat insulation application under extreme humidity and high-heat environments is realized.
2. The invention provides a new strategy for preparing gel emulsion based on ethyl cellulose as a stabilizer, adopts a gel emulsion template method, realizes the conversion from soft substances to polymer aerogel through free radical initiated polymerization, and ensures that the gel emulsion stabilizer nanofiber not only meets the advantages of a micromolecule gelatinization agent, but also can avoid complex synthesis.
3. The gel emulsion template method used in the invention expands the volume fraction range of the internal phase on the basis of using a novel stabilizer, and simultaneously hollow glass microspheres can be added in the preparation process of the aerogel precursor to enhance the mechanical property of the aerogel and endow the aerogel with corresponding performance.
4. According to the invention, the water-insoluble ethyl cellulose is used as a gel emulsion stabilizer, the long-chain polymer is reduced from the commonly reported dosage of 5% -20% to 1% -2%, the gel emulsion can be efficiently and stably formed, the high-molecular rigid monomer styrene and the two-end and three-end ethylenic crosslinking agents are introduced into the oil phase of a gel emulsion system, and the aerogel material with adjustable porosity, density, strength and heat conductivity coefficient can be obtained in a large range by adjusting the oil-water ratio in the system.
5. According to the invention, the gel emulsion is prepared by taking the ethyl cellulose as the stabilizer, the internal phase volume fraction of the traditional gel emulsion is more than 74% to form a stable emulsion system, and the stabilizer breaks through the limit that the internal phase volume fraction is lower than 74% through research, so that the application range of a gel emulsion template method is widened.
6. The density of the highly open-pore light heat insulation aerogel prepared by the invention is only 40mg/cm 3～240mg/cm3, the dandelion cannot be deformed when the aerogel is placed on soft dandelion, the mechanical property is excellent, and the heat conductivity coefficient can reach 23 mW/(m.K) at the lowest.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a schematic illustration of the process of preparing a porous polymer aerogel according to the present invention.
Fig. 2 is a graph of contact angle measurements of porous polymer aerogel blocks prepared in accordance with example 8 of the present invention.
FIG. 3 is a diagram showing the steps of dropping copper sulfate aqueous solution onto the porous polymer aerogel monolith prepared in example 8 of the present invention.
Fig. 4 is a physical diagram of a porous polymer aerogel block prepared in example 8 of the present invention placed on dandelion.
FIG. 5 is a scanning electron microscope image of a porous polymer aerogel block prepared in example 8 of the present invention.
FIG. 6 is a scanning electron microscope image of a cross section of a porous polymer aerogel block prepared in accordance with example 8 of the present invention.
FIG. 7 is a stress-strain diagram of a porous polymer aerogel block prepared in accordance with example 8 of the present invention.
FIG. 8 is a graph showing the pore size distribution of a porous polymer aerogel block prepared in accordance with example 8 of the present invention.
FIG. 9 is a schematic structural diagram of a high temperature insulation test of the lightweight insulating aerogel material prepared in example 8 of the present invention.
FIG. 10 is a schematic view showing the effect of the high-temperature insulation test of the lightweight insulating aerogel material prepared in example 8 of the present invention.
FIG. 11 is a graphical representation of the high temperature insulation test of the lightweight insulating aerogel material prepared in example 8 of the present invention as a function of time.
FIG. 12 is a schematic structural diagram of a lightweight insulating aerogel material prepared by performing an amplification test using the method of example 8 of the present invention.
FIG. 13 is a graph of the rheological properties of the lightweight insulating aerogel materials prepared in examples 1-8 according to the present invention.
Detailed Description
Fig. 1 is a schematic diagram of a process for preparing a porous polymer aerogel according to the present invention, and as can be seen from fig. 1, after mixing an oil phase and a water phase, the oil phase and the water phase are incompatible, and form an interface therebetween, and after performing oscillation mixing, a gel emulsion is formed, and the nanofiber, i.e., the ethylcellulose, and the hollow nanoparticle, i.e., the hollow glass microsphere, are crosslinked, and then polymerized and dried, thereby obtaining the porous polymer aerogel.
Example 1
The embodiment comprises the following steps:
Step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 4mg of ethyl cellulose, 2mg of azobisisobutyronitrile and 20mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 500 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 4 hours at 40 ℃, then raising the temperature to 80 ℃ for further polymerization for 20 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.24g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Example 2
The embodiment comprises the following steps:
Step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 4mg of ethyl cellulose, 2mg of azobisisobutyronitrile and 20mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 1000 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 4 hours at 40 ℃, then raising the temperature to 80 ℃ for further polymerization for 20 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.16g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Example 3
The embodiment comprises the following steps:
Step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 4mg of ethyl cellulose, 2mg of azobisisobutyronitrile and 20mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 1500 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 4 hours at 40 ℃, then raising the temperature to 80 ℃ for further polymerization for 20 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.14g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Example 4
The embodiment comprises the following steps:
step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 4mg of ethyl cellulose, 2mg of azobisisobutyronitrile and 20mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 2000 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 4 hours at 40 ℃, then raising the temperature to 80 ℃ for further polymerization for 20 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.11g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Example 5
The embodiment comprises the following steps:
step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 4mg of ethyl cellulose, 2mg of azobisisobutyronitrile and 20mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 2500 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 4 hours at 40 ℃, then raising the temperature to 80 ℃ for further polymerization for 20 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.10g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Example 6
The embodiment comprises the following steps:
step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 4mg of ethyl cellulose, 2mg of azobisisobutyronitrile and 20mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 3000 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 4 hours at 40 ℃, then raising the temperature to 80 ℃ for further polymerization for 20 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.056g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Example 7
The embodiment comprises the following steps:
step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 4mg of ethyl cellulose, 2mg of azobisisobutyronitrile and 20mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 3500 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 4 hours at 40 ℃, then raising the temperature to 80 ℃ for further polymerization for 20 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.05g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Example 8
The embodiment comprises the following steps:
Step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 4mg of ethyl cellulose, 2mg of azobisisobutyronitrile and 20mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 4000 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 4 hours at 40 ℃, then raising the temperature to 80 ℃ for further polymerization for 20 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.04g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Fig. 2 is a graph of contact angle test of the porous polymer aerogel block prepared in this example, and as can be seen from fig. 2, the contact angle is about 134 ° by using a contact angle tester to characterize the affinity of the porous polymer aerogel block prepared in this example.
Fig. 3 is a physical diagram of the porous polymer aerogel block prepared in this example, in which the copper sulfate aqueous solution is dropped on the surface of the material, and as can be seen from fig. 3, the copper sulfate aqueous solution does not infiltrate into the interior of the material.
Fig. 4 is a physical diagram of the porous polymer aerogel block prepared in this embodiment placed on dandelion, and as can be seen from fig. 4, the density of the material is very low, and the porous polymer aerogel block is placed on dandelion and cannot deform.
Fig. 5 is a scanning electron microscope image of a porous polymer aerogel block prepared in this embodiment, and as can be seen from fig. 5, the internal structure of the block is highly open-pore, and shows a multi-level pore structure distribution, and meanwhile, the nano microspheres can be seen to hang on the pore wall, so that the mechanical strength of the material is enhanced.
Fig. 6 is a scanning electron microscope image of a cross section of a porous polymer aerogel block prepared in this example, and as can be seen from fig. 6, the material is through from top to bottom and has good permeability.
Fig. 7 is a stress-strain diagram of the porous polymer aerogel block prepared in this example, and it can be seen from fig. 7 that the compressive strength of the block at a deformation of 5% is 1.0MPa.
FIG. 8 is a graph showing pore size distribution of the porous polymer aerogel block prepared in this example, and as can be seen from FIG. 8, the average pore size distribution is 10. Mu.m, and the measurement results correspond to the pore size of the scanning electron microscope.
Fig. 9 is a schematic structural diagram of a high-temperature heat insulation test of the light-weight heat insulation aerogel material prepared in this embodiment, fig. 10 is a schematic structural diagram of a high-temperature heat insulation test of the light-weight heat insulation aerogel material prepared in this embodiment, fig. 11 is a schematic diagram of a time change of the high-temperature heat insulation test of the light-weight heat insulation aerogel material prepared in this embodiment, and as can be seen from fig. 9, fig. 10 and fig. 11, the light-weight heat insulation aerogel material is still kept dry under extremely high humidity and hot water vapor, and meanwhile, the aerogel is placed on a heating plate at 310 ℃ for more than 1 hour, the temperature at the upper end of the material is only 63 ℃, which indicates that the heat conductivity coefficient of the material is very low, and has a good heat insulation effect.
FIG. 12 is a schematic structural view of a lightweight insulating aerogel material prepared by performing an enlargement test using the method of this example, and it can be seen from FIG. 12 that the lightweight insulating aerogel material prepared by performing an enlargement test has a complete structure.
Fig. 13 is a graph showing the rheological properties of the lightweight thermal insulation aerogel materials prepared in examples 1-8 according to the present invention, as can be seen from fig. 13, under the test condition of room temperature, the rheological properties of the gel emulsions with different water contents are hardly greatly affected, and the ethyl cellulose used in this time has almost 5% -20% or even higher content when being used as a gel emulsion stabilizer in the previous literature report, however, the content can be found to be 1% -2% for the first time in the present invention, the minimum limit reported at home and abroad is broken through, the internal phase volume fraction of the traditional gel emulsion must be greater than 74% to form the gel emulsion, the system explored by the present invention can be as low as 70% to form a stable gel emulsion, the water content of the gel emulsion can be controlled in a large range from 70% -95%, the breakthrough of the internal phase volume of the gel emulsion is wide in application range, the water content plays a role in the density and the porosity of the porous aerogel material by initiating the continuous phase polymerization, the increase of the water content can effectively reduce the internal phase volume of the gel emulsion, and the porosity coefficient of the porous material is reduced at the same time.
Example 9
The embodiment comprises the following steps:
Step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 2mg of ethyl cellulose, 1mg of azobisisobutyronitrile and 30mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a refiner, dropwise adding 4000 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting a biased white gel emulsion, standing, inverting a test tube, observing, and losing fluidity of the system to obtain a gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 6 hours at 35 ℃, then raising the temperature to 60 ℃ for further polymerization for 10 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
Preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 90 ℃ at a heating rate of 1 ℃/min, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is not 0.04g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
Example 10
The embodiment comprises the following steps:
Step one, preparing a gel emulsion system: mixing 150 mu L of styrene, 40 mu L of divinylbenzene and 20 mu L of ethylene glycol dimethacrylate at room temperature to obtain an oil phase, adding 3mg of ethyl cellulose, 1.5mg of azobisisobutyronitrile and 10mg of hollow glass microspheres into the oil phase, performing ultrasonic treatment, putting the ultrasonic treated product into a homogenizer, dropwise adding 4000 mu L of distilled water, performing high-speed oscillation, observing that the obtained mixture is highly viscous, presenting off-white gel emulsion, standing, inverting a test tube, observing that the system loses fluidity, and obtaining gel emulsion;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath pan to perform prepolymerization for 5 hours at 45 ℃, then raising the temperature to 85 ℃ for further polymerization for 15 hours, and then washing and drying the product at normal temperature by using absolute ethyl alcohol in sequence to obtain a porous polymer aerogel block material with ultra-low density;
Preparing an ethyl cellulose stable light heat insulation aerogel material: and (3) placing the aerogel block material obtained in the step (II) into a tube furnace, heating to 110 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain the light heat insulation aerogel material.
According to detection, the density of the ultra-low density porous polymer aerogel block prepared in the embodiment is 0.04g/cm -3, the porosity is not less than 95%, the density of the prepared light heat insulation aerogel material is 40mg/cm 3～240mg/cm3, and the heat conductivity coefficient is not less than 23 mW/(m.K).
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (5)
1. A method for preparing ethyl cellulose stabilized light insulating aerogel, which is characterized by comprising the following steps:
Step one, preparing a gel emulsion system: under the condition of room temperature, mixing a polymerizable monomer and a cross-linking agent to obtain an oil phase, adding ethyl cellulose, azodiisobutyronitrile and hollow glass beads into the oil phase, performing ultrasonic treatment, and adding a water phase to perform high-speed oscillation to obtain gel emulsion; the polymerizable monomer is styrene, and the crosslinking agent is divinylbenzene and ethylene glycol dimethacrylate; the mass fraction of styrene in the oil phase is 71.4%, the mass fraction of ethylene glycol dimethacrylate is 9.5%, the balance is divinylbenzene, the mass of ethyl cellulose is 1% -2% of the volume of the oil phase, the mass of azodiisobutyronitrile is 1% -2% of the volume of the oil phase, the mass of the hollow glass beads is 1% -3% of the volume of the oil phase, wherein the mass unit is mg, and the volume unit is mu L; the volume ratio of the oil phase to the water phase is 210:500-4000, and the water phase is distilled water;
Step two, preparing porous polymer aerogel blocks with ultra-low density: introducing nitrogen into the gel emulsion obtained in the step one, then placing the gel emulsion into an oil bath for polymerization, and then washing and drying the product at normal temperature in sequence to obtain a porous polymer aerogel block material with ultra-low density;
Preparing an ethyl cellulose stable light heat insulation aerogel material: placing the aerogel block material obtained in the second step into a tube furnace for heating, and naturally cooling to room temperature to obtain a light heat insulation aerogel material; the heating process is as follows: heating to 90-110 ℃ at a heating rate of 1-3 ℃/min, and then preserving heat for 1-2 h.
2. The method for preparing the ethylcellulose stable light weight insulating aerogel as set forth in claim 1, wherein in step one, the process of adding the aqueous phase is as follows: the sonicated product was placed in a homogenizer and then the aqueous phase was added dropwise.
3. The method for preparing the ethylcellulose stable light weight insulating aerogel as set forth in claim 1, wherein in the step two, the polymerization process is as follows: prepolymerizing for 4-6 h at 35-45 ℃, and then further polymerizing for 10-20 h by raising the temperature to 60-85 ℃.
4. The method for preparing a lightweight, ethylcellulose-stabilized aerogel as claimed in claim 1, wherein said ultra-low density porous polymer aerogel block in step two has a density of no greater than 0.04g/cm 3 and a porosity of no less than 95%.
5. The method for preparing the ethylcellulose stable light weight insulating aerogel as claimed in claim 1, wherein in the third step, the density of the light weight insulating aerogel material is 40mg/cm 3~240mg/cm3, and the thermal conductivity is not less than 23 mW/(m-K).
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