CN117661371A - Preparation method of silica nano aerogel heat insulation paper - Google Patents
Preparation method of silica nano aerogel heat insulation paper Download PDFInfo
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- CN117661371A CN117661371A CN202311642075.5A CN202311642075A CN117661371A CN 117661371 A CN117661371 A CN 117661371A CN 202311642075 A CN202311642075 A CN 202311642075A CN 117661371 A CN117661371 A CN 117661371A
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- aerogel
- silica
- heat insulation
- fiber
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000004964 aerogel Substances 0.000 title claims abstract description 77
- 238000009413 insulation Methods 0.000 title claims abstract description 57
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 66
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000011229 interlayer Substances 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 230000005484 gravity Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000499 gel Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 230000029936 alkylation Effects 0.000 claims description 7
- 238000005804 alkylation reaction Methods 0.000 claims description 7
- 238000005192 partition Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 239000011240 wet gel Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229920002334 Spandex Polymers 0.000 claims description 2
- 229920004933 Terylene® Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000004759 spandex Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 230000008384 membrane barrier Effects 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 7
- 239000002657 fibrous material Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003365 glass fiber Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method of silica nano aerogel heat insulation paper, which comprises the following steps: (1) coating a permeable membrane interlayer on the surface of each piece of fiber paper; (2) preparing a silicon dioxide aerogel prepolymer mixed solution; (3) Compounding the silica aerogel prepolymer mixed solution with fiber paper to obtain wet silica aerogel paper; (4) The wet silica aerogel paper is subjected to solvent displacement, hydrophobic modification and drying. According to the invention, the aerogel paper is prepared by coating the surface of the fiber paper with the permeable membrane interlayer and applying gravity in the gelling process, so that the problems that aerogel is fragile and fiber materials are low in strength, the prepared ultrathin aerogel paper (less than or equal to 0.3 mm) is fragile are solved, the gel absorption amount of the fiber paper is effectively controlled, and the flatness, thickness and thickness dimension deviation of the aerogel paper are ensured; the prepared silica nano aerogel heat insulation paper has a smooth appearance and has no defects of crease, hole, crack and the like affecting the use.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of silica nano aerogel heat insulation paper.
Background
The silica nano aerogel heat insulation paper is a heat insulation material formed by compounding aerogel and fiber paper, has the advantages of ultra-thin, ultra-light, good flexibility, convenient construction, easy cutting and processing and the like besides the advantages of aerogel, and particularly has the advantages of high-efficiency heat insulation performance and ultra-thin thickness, is particularly suitable for heat insulation of complex parts and high-temperature narrow spaces, and can be widely used for heat insulation and heat insulation of batteries, fighter engines and precision equipment.
Most aerogel papers in the current market are made by two methods:
one method is aerogel paper prepared by directly blending aerogel powder and fibers and then drying. In the method, in order to uniformly compound aerogel powder and fibers, various additives such as polyaluminum chloride, sodium silicate, silane coupling agents or adhesives are needed, so that the cost of the aerogel paper is increased, and because many of the additives are high-temperature volatile components, volatile pollution is easily caused to the environment; the particle size of the aerogel powder needs to be strictly controlled, and is generally 100nm or less. Although the aerogel paper prepared by the method has a thinner thickness, the aerogel paper has poorer heat insulation performance and stability because of the problems of structural collapse and uneven dispersion of the aerogel powder in the soaking process.
Another method is to impregnate a composite aerogel sol with a roll of fibrous mat and fibrous paper, and then dry to produce the aerogel paper. The method has the following characteristics: the sol and the coiled fiber mat or fiber paper can be uniformly compounded only after being immersed for a long time (generally 2-10 hours or even longer time), and if the time is too short, the heat insulation performance of the aerogel paper can not be ensured; drying conditions below 100 ℃ and normal pressure cannot ensure drying effect, so that drying needs to be performed under the conditions of higher temperature (generally above 240 ℃) and higher pressure (generally above 7.5 MPa), and the complexity of the process is increased. Although the aerogel paper prepared by the method can obtain excellent heat insulation performance, the aerogel paper is uneven in thickness and easy to damage, and meanwhile, the manufacturing time is long, the manufacturing process is complex, so that the cost of the product aerogel paper is high.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of silica nano aerogel heat insulation paper.
The preparation method of the silica nano aerogel heat insulation paper comprises the following steps:
(1) The surface of each piece of fiber paper is covered with a permeable membrane interlayer, the permeable membrane interlayer is one or more than two non-woven fabrics of polypropylene fiber, terylene, cotton fiber, spandex and acrylic fiber which have the characteristics of water repellency, air permeability, flexibility, flame retardance, no toxicity, no irritation and the like, the permeable membrane interlayer is one or two of glass fiber, high silica fiber, ceramic fiber, alumina fiber and mullite fiber, and the fiber paper can be a sheet material or a coiled material through any one of rolling, hot pressing and vacuum pressing.
(2) Preparing a silicon dioxide aerogel prepolymer mixed solution, which comprises the following steps:
A. mixing a silicon source, a solvent, water and a weak acid catalyst, and stirring for 30min;
B. adding a two-phase adhesive in the step A, and stirring for 5min;
C. and B, adding an alkaline catalyst into the mixture in the step, and stirring the mixture for 5 minutes to obtain the catalyst.
(3) And compounding the silica aerogel prepolymer mixed solution with fiber paper to obtain wet silica aerogel paper.
(4) And performing solvent replacement, hydrophobic modification and drying on the wet silica aerogel paper to obtain the silica nano aerogel heat insulation paper, wherein supercritical drying, normal pressure drying or freeze drying can be selected for drying.
Further, the ratio of the silicon source, the solvent, the water, the weak acid catalyst, the two-phase adhesive and the alkaline catalyst is 1: (2-10): (0.05-0.15): (0.0005-0.0015): (0.15-0.75): (0.01-0.1); the silicon source is ethyl orthosilicate or methyl orthosilicate; the solvent is methanol or ethanol; the water is purified water or distilled water; the weak acid catalyst is boric acid, oxalic acid or phosphoric acid; the two-phase adhesive is one or two of silica gel and fumed silica; the alkaline catalyst is one or the combination of more than two of ammonia water, ammonium fluoride, formamide and dimethylformamide.
Further, the silica aerogel prepolymer mixed solution and the fiber paper are compounded, namely the fiber paper is placed in a gel tool, the fiber paper is soaked in the silica aerogel prepolymer mixed solution through a vacuum pump, then the gel tool is placed on an ultrasonic vibration table or a mechanical wave vibration table, the vibration frequency of the vibration table is 40-80Hz, after 5-20min of operation, the weight of the wet gel paper (namely the sum of the weight of the fiber paper and the weight of the silica aerogel prepolymer mixed solution) is applied to the fiber paper for 0.1-0.5 times of the weight, then the vibration table is closed after the operation is continued for 10-30min, and the fiber paper is kept stand for 2-24h.
When the fiber paper is a sheet material and the thickness is not more than 0.5mm, in order to ensure the flatness and the integrity of the fiber material, before solvent replacement is carried out on the wet silica aerogel paper, a permeable membrane interlayer on the surface of the fiber paper is removed, when the fiber paper is a sheet material with the thickness of more than 0.5mm, the permeable membrane interlayer is not required to be removed, the wet silica aerogel paper is placed on a tooling partition plate uniformly distributed with meshes during solvent replacement, the gravity which is 0.01-0.1 times of the weight of the wet silica aerogel paper of each layer of partition plate is applied, and then the wet silica aerogel paper is placed in a solvent, and is replaced for 4-24 hours at the temperature of 40-65 ℃.
When the fibrous paper is a roll, the permeation membrane interlayer does not need to be removed, and the solvent replacement is to put wet silica aerogel paper into a solvent and replace the wet silica aerogel paper for 4 to 24 hours at the temperature of 40 to 65 ℃.
Further, the hydrophobic modification is to put wet silica aerogel paper subjected to solvent replacement into a hydrophobic alcohol solution, and react for 4-24 hours at the temperature of 40-65 ℃ to carry out alkylation in-situ chemical reaction, wherein the hydrophobic agent is one of alkylation reagents such as hexamethyldisilazane, trimethylmethoxysilane, trimethylchlorosilane and the like.
Compared with the prior art, the preparation method of the silica nano aerogel heat insulation paper has the beneficial effects that: 1. according to the invention, the aerogel paper is prepared by coating the surface of the fiber paper with the permeable membrane interlayer and applying gravity in the gelling process, so that the problems that aerogel is fragile and the strength of fiber materials is low, and the prepared ultrathin aerogel paper (less than or equal to 0.3 mm) is fragile are solved, the gel absorption amount of the fiber paper is effectively controlled, the strength of the fiber paper is improved, and the integrity, flatness, deformation, thickness and thickness dimension deviation of the aerogel paper are ensured;
2. according to the invention, through adding a permeable membrane interlayer and a spacer interlayer on the surface of the fiber paper, and matching with an ultrasonic wave or mechanical wave permeable flow increasing technology in the aerogel paper gel forming process, the permeability of the silica aerogel prepolymer solution in the multi-layer fiber paper is enhanced, so that the prepolymer solution is uniformly loaded on the surface of the fiber paper; the collision strength and the collision frequency between rubber particles are enhanced by utilizing the transverse wave vibration action and the longitudinal wave vibration action of ultrasonic waves or mechanical waves, and the agglomeration structure among the rubber particles is destroyed, so that the growth of the rubber particles is complete; meanwhile, the surface tension among water molecules is destroyed, the activity of the water molecules is improved, the growth of colloidal particles is accelerated to form a micelle, the composite efficiency of fiber paper and a silica aerogel prepolymer is improved, and the traditional impregnation time is shortened from 2-10h to 15-50min;
3. according to the invention, the two-phase adhesive (silica gel and gas phase silica) is added into the mixed liquid of the silica aerogel prepolymer, so that the high tensile strength can be born under the condition that the heat insulation performance is not affected, because-OH in the two-phase adhesive is connected with silica aerogel particles to form a ≡Si-O-Si ≡network structure, the gaps between fiber reinforcements are filled, the gaps between the silica aerogel particles and the fibers are reduced, the silica aerogel particles are tightly and firmly anchored on the surface of the fiber paper, the compactness of the microstructure of the composite material is greatly improved, the collapse of the silica aerogel is prevented, the vibration mass loss rate is reduced, and the mechanical property of the composite material is further enhanced; in addition, the macropores of the two-phase adhesive can contain part of silica hydrosol or aerogel particles in the mixing process, so that the macropores in the two-phase adhesive are divided into small holes, the porous structure of the silica aerogel is finally strengthened, and the heat insulation performance of the material is enhanced;
4. the invention adopts boric acid as a hydrolysis catalyst, and as boron in the boric acid is an electron-deficient atom, hydroxyl ions of water molecules can be added to release protons, and after a silicon source is hydrolyzed to form a polyhydroxy compound intermediate, the acidity of the polyhydroxy compound intermediate is enhanced by utilizing the electron-deficient property, and the further hydrolysis of the silicon source is promoted in turn; meanwhile, in the hydrolysis process of the silicon source, the boric acid can reduce the viscosity and the surface tension of the mixed solution, improve the refractive index of the mixed solution, improve the heat insulation and the transparency of the aerogel paper, and finally improve the heat insulation, the chemical stability, the mechanical impact resistance and the thermal shock resistance of the aerogel paper; in addition, boric acid does not bring new elements to the gel paper, and the risk brought by strong acid can be reduced, because the strong acid has larger harm to human bodies and stronger corrosiveness to equipment;
5. the invention can prepare the aerogel paper with the minimum thickness of only 0.1mm, and can be almost applied to all occasions needing heat insulation and heat preservation through single use or superposition of the aerogel paper; meanwhile, the super-strong adsorption performance of the aerogel can be utilized to be applied to separation chromatography and serve as a carrier;
6. the silica nano aerogel heat insulation paper prepared by the method has a smooth appearance, has no defects of crease, hole, crack and the like affecting use, and shortens the impregnation time.
Drawings
The invention is described in further detail below with reference to the accompanying drawings.
FIG. 1 is a physical diagram of silica nano aerogel thermal insulation paper prepared in example 1;
FIG. 2 is a physical diagram I of the silica nano aerogel thermal insulation paper prepared in comparative example 1;
FIG. 3 is a second physical diagram of the silica aerogel thermal insulation paper prepared in comparative example 1;
FIG. 4 is a three-dimensional view of silica aerogel thermal insulation paper prepared in comparative example 1;
FIG. 5 is a physical diagram of silica nano aerogel thermal insulation paper prepared in example 2;
FIG. 6 is a physical diagram I of the silica nano aerogel thermal insulation paper prepared in comparative example 2;
fig. 7 is a physical diagram two of the silica nano aerogel thermal insulation paper prepared in comparative example 2.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
It should be noted that the term "comprises," "comprising," or any other variation thereof is intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
The preparation method of the silica nano aerogel heat insulation paper comprises the following steps:
(1) The surface of each glass fiber paper with 0.27mm is covered with a glass fiber paper with the surface density of 30 g/m by adopting a rolling mode 2 Cutting into sheets of 400mm×400mm, overlapping the treated glass fiber paper in a gel fixture, adding a layer of polyester spiral silk screen with the thickness of 2mm every 8cm, overlapping in sequence, and stopping when the glass fiber paper is mounted at the height of 3/4 of the gel fixture.
(2) Mixing 1 part of tetraethoxysilane, 6 parts of methanol, 0.07 part of purified water and 0.00075 part of boric acid, stirring for 30min, adding 0.35 part of silica gel, uniformly mixing, stirring for 5min, adding 0.045 part of ammonia water, uniformly mixing, and continuously stirring for 5min to obtain a silica aerogel prepolymer mixed solution.
(3) The mixed solution of the silica aerogel prepolymer is pumped by a vacuum pump to penetrate through the uppermost layer of fiber paper, a mechanical wave vibration table is started, the vibration frequency is 65 Hz, after the operation is carried out for 15min, the gravity which is 0.25 times of the weight of the wet gel paper is applied to the fiber paper, after the operation is continued for 15min, the vibration table is closed, and the fiber paper is kept stand for 12h; in order to ensure the flatness and integrity of the fiber material, the permeable membrane interlayer on the surface of the fiber paper is removed, and the polyester spiral silk screen is reserved.
(4) Placing wet silica aerogel paper on tooling partition boards uniformly provided with meshes, applying gravity which is 0.1 times of the weight of the wet silica aerogel paper on each layer of partition boards, placing the wet silica aerogel paper and the tooling together into 99% methanol solvent, and replacing the solvent for 20 hours at 55 ℃; then putting the mixture into hexamethyldisilazane alcohol solution, and carrying out alkylation in-situ chemical reaction for 8 hours at 55 ℃; and then carrying out supercritical carbon dioxide drying to obtain the silica nano aerogel heat insulation paper.
The silica nano aerogel heat insulation paper prepared by the embodiment has a smooth appearance and has no defects of crease, hole, crack and the like affecting the use. The thickness is 0.36-0.41mm; bulk Density (g/cm) 3 ) 0.23-0.25; the heat conductivity coefficient (25 ℃) is 0.0173-0.0183 (W/(m.K); tensile strength (machine direction) (kN/m) of 0.86-0.92; high and low temperature resistance (-55-600deg.C, 1 h); the hydrophobicity rate is more than or equal to 98 percent; the thermal weight loss rate at 600 ℃ is less than or equal to 3.0 percent, and the bending performance is crack-free and breakage-free; rate of loss of vibrating massLess than or equal to 0.5 percent; the qualification rate of paper products is more than or equal to 90 percent. The main detection results are shown in Table 1, and the specific real objects are shown in FIG. 1.
TABLE 1 third party test data for silica aerogel thermal insulation paper (multiple sheets) -example 1
Comparative example 1
The glass fiber paper with the thickness of 0.27mm and the thickness of 400mm multiplied by 400mm is overlapped in a gel tool, a layer of polyester spiral silk screen with the thickness of 2mm is added every 8cm, and the mixture is sequentially overlapped and is stopped when being mounted at the height of 3/4 of the gel tool. The rest of the procedure is the same as in example 1.
The silica nano aerogel heat insulation paper prepared by the comparative example has the defects of wrinkling, hole breaking, cracking, serious deformation, uneven thickness and the like which affect the use; the thickness is 0.28-0.71mm; bulk Density (g/cm) 3 ) 0.19-0.30; the heat conductivity (25 ℃ C.) (W/(m.K)) is 0.019-0.031; the tensile strength (longitudinal direction) (kN/m) is 0.58-0.76, the single sheet has poor local permeation or partial hydrophobicity, and the vibration mass loss rate is more than or equal to 5 percent. The main detection results are shown in Table 2, and the specific examples are shown in FIG. 2, FIG. 3 and FIG. 4.
Table 2 third party test data for silica aerogel thermal insulation paper (multiple sheets) -comparative example 1
In comparative example 1, since the surface of the fiber paper is not covered, two pieces of the fiber paper are bonded together, and after the preparation is completed, separation is difficult and the fiber paper is easily torn; in addition, as the surface of the fiber paper is not covered with the film, the quantity of the aerogel on the fiber paper is different, the aerogel close to the outer layer and the surface is more, and the aerogel on the fiber paper in the inner layer and the center is less or even has the local non-glue condition.
Example 2
The preparation method of the silica nano aerogel heat insulation paper comprises the following steps:
(1) The surface of a piece of glass fiber paper with the thickness of 0.08mm is covered with a paper with the surface density of 30 g/m by adopting a rolling mode 2 And cutting the polypropylene fiber non-woven fabric into sheets with the thickness of 300mm multiplied by 300mm, and then placing the treated glass fiber paper into a gel tool.
(2) Mixing 1 part of tetraethoxysilane, 8 parts of methanol, 0.05 part of purified water and 0.001 part of boric acid, stirring for 30min, adding 0.5 part of fumed silica, uniformly mixing, stirring for 5min, adding 0.075 part of ammonia water, uniformly mixing, and continuously stirring for 5min to obtain a silica aerogel prepolymer mixed solution.
(3) The mixed solution of the silica aerogel prepolymer is pumped by a vacuum pump to permeate the fiber paper, a mechanical wave vibration table is started, the vibration frequency is 60 Hz, after 10 minutes of operation, the gravity which is 0.2 times of the weight of the wet gel paper is applied to the fiber paper, after 10 minutes of operation, the vibration table is closed, and the fiber paper is kept stand for 30 minutes, so that the flatness and the integrity of the fiber material are ensured, and the permeable membrane interlayer on the surface of the fiber paper is removed.
(4) Placing wet silica aerogel paper on a tooling partition board uniformly provided with meshes, applying the gravity which is 0.1 times of the weight of the wet silica aerogel paper on the wet silica aerogel paper, placing the wet silica aerogel paper and the tooling together into 99% methanol solvent, and replacing the solvent for 4 hours at 50 ℃; then putting the mixture into hexamethyldisilazane alcohol solution, and carrying out alkylation in-situ chemical reaction for 4 hours at 55 ℃; and then carrying out supercritical carbon dioxide drying to obtain the silica nano aerogel heat insulation paper.
The silica nano aerogel heat insulation paper prepared by the embodiment has a smooth appearance and has no defects of crease, hole, crack and the like affecting use; bulk density of 0.215g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The thermal conductivity (25 ℃) is 0.0164W/(m.K); tensile strength (machine direction) of 0.28-0.32kN/m; high and low temperature resistance (-55-600deg.C, 1 h); the hydrophobicity is 98.9%; the thermal weight loss rate at 600 ℃ is 2.72 percent, and the bending performance is crack-free and breakage-free; the loss rate of the vibration mass was 0.5%. One sample was taken on the same piece of paper in each of the length, width and center positions, the thickness detection results are shown in table 3, and the specific physical photographs are shown in fig. 5.
TABLE 3 third party test data for silica aerogel thermal insulation paper (Single sheet) example 2
Comparative example 2
A piece of glass fiber paper with the thickness of 0.08mm and the thickness of 300X 300mm is put into a gel tooling, and the rest operation steps are the same as in example 2.
The silica nano aerogel heat insulation paper prepared by the comparative example has the defects of wrinkling, hole breaking, cracking, serious deformation, uneven thickness and the like which affect the use; bulk density of 0.295g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The thermal conductivity (25 ℃ C.) is 0.0188W/(m.K); tensile strength (machine direction) of 0.18-0.29kN/m; the single sheet has poor local permeation or partial hydrophobicity, and the loss rate of vibration mass is 4.58%. The length, width and center position of the same piece of paper are respectively measured to obtain one sample, the thickness detection results are shown in table 4, and specific physical photos are shown in fig. 6 and 7.
TABLE 4 third party test data for silica aerogel Heat insulation paper (Single sheet) comparative example 2
In comparative example 2, since the surface of the fiber paper is not coated, the sol is deposited on the surface of the fiber paper, resulting in excessive surface colloid and uneven thickness. In addition, as the surface of the fiber paper is not covered with the film, the fiber material is brittle, so that the aerogel fiber paper has holes and cracks.
Example 3
The preparation method of the silica nano aerogel heat insulation paper comprises the following steps:
(1) The high silica fiber paper with the length of 70m and the thickness of 0.26mm is covered with the surface density of 20 g/m by adopting a rolling mode 2 And then coiling, and then placing the rolled high silica fiber paper into a gel tool.
(2) Mixing 1 part of tetraethoxysilane, 5 parts of methanol, 0.06 part of purified water and 0.00065 part of boric acid, stirring for 30min, adding 0.25 part of fumed silica, uniformly mixing, stirring for 5min, adding 0.065 part of ammonia water, uniformly mixing, and continuously stirring for 5min to obtain a silica aerogel prepolymer mixed solution.
(3) The mixed solution of the silica aerogel prepolymer is pumped by a vacuum pump to be about 5mm through the fiber paper, a mechanical wave vibration table is started, the vibration frequency is 80Hz, after the operation is carried out for 20min, the gravity which is 0.1 time of the weight of the wet gel paper is applied to the fiber paper, after the operation is continued for 30min, the vibration table is closed, and the fiber paper is kept stand for 18h.
(4) Putting the coiled wet gel paper into 99% methanol solvent, and performing solvent replacement for 24 hours at 55 ℃; then putting the mixture into a trimethylmethoxy silanol solution, and carrying out alkylation in-situ chemical reaction for 8 hours at 55 ℃; and then carrying out supercritical carbon dioxide drying to obtain the silica nano aerogel heat insulation paper.
The silica nano aerogel heat insulation paper prepared by the embodiment has a smooth appearance and has no defects of crease, hole, crack and the like affecting use; the thickness is 0.32-0.36mm; bulk Density (g/cm) 3 ) Less than or equal to 0.3; the heat conductivity coefficient (W/(m.K)) is less than or equal to 0.021; tensile strength (longitudinal direction) (kN/m) is more than or equal to 0.35; high and low temperature resistance (-55-600deg.C, 1 h); the hydrophobicity rate is more than or equal to 98 percent; the thermal weight loss rate at 600 ℃ is less than or equal to 3.0 percent, and the bending performance is crack-free and breakage-free; the loss rate of the vibration mass is less than or equal to 0.5%; the qualification rate of paper products is more than or equal to 91 percent. The main detection results are shown in Table 5.
TABLE 5 third party test data for silica aerogel Heat insulation paper (coiled Material) -example 3
Other aspects of the invention are well known to those skilled in the art.
The protection scope of the present invention is not limited to the technical solutions disclosed in the specific embodiments, and any modification, equivalent replacement, improvement, etc. made to the above embodiments according to the technical substance of the present invention falls within the protection scope of the present invention.
Claims (10)
1. A preparation method of silica nano aerogel heat insulation paper is characterized by comprising the following steps: the method comprises the following steps:
(1) Coating a permeable membrane interlayer on the surface of each piece of fiber paper;
(2) Preparing a silicon dioxide aerogel prepolymer mixed solution;
(3) Compounding the silica aerogel prepolymer mixed solution with fiber paper to obtain wet silica aerogel paper;
(4) And performing solvent replacement, hydrophobic modification and drying on the wet silica aerogel paper to obtain the silica nano aerogel heat insulation paper.
2. The method for preparing the silica nano aerogel heat insulation paper according to claim 1, which is characterized in that: the permeable membrane interlayer is one or more than two non-woven fabrics of polypropylene, terylene, cotton, spandex and acrylic, and is coated on the surface of the fiber paper by any one of rolling, hot pressing and vacuum pressing.
3. The method for preparing the silica nano aerogel heat insulation paper according to claim 2, which is characterized in that: the silica aerogel prepolymer mixed solution is prepared by the following steps:
A. mixing a silicon source, a solvent, water and a weak acid catalyst, and stirring for 30min;
B. adding a two-phase adhesive in the step A, and stirring for 5min;
C. and B, adding an alkaline catalyst into the mixture in the step, and stirring the mixture for 5 minutes to obtain the catalyst.
4. The method for preparing the silica nano aerogel thermal insulation paper according to claim 3, wherein: the ratio of the silicon source, the solvent, the water, the weak acid catalyst, the two-phase adhesive and the alkaline catalyst is 1: (2-10): (0.05-0.15): (0.0005-0.0015): (0.15-0.75): (0.01-0.1); the silicon source is ethyl orthosilicate or methyl orthosilicate; the solvent is methanol or ethanol; the water is purified water or distilled water; the weak acid catalyst is boric acid, oxalic acid or phosphoric acid; the two-phase adhesive is one or two of silica gel and fumed silica; the alkaline catalyst is one or the combination of more than two of ammonia water, ammonium fluoride, formamide and dimethylformamide.
5. The method for preparing the silica nano aerogel heat insulation paper according to claim 4, which is characterized in that: the method comprises the steps of placing a gel tool on an ultrasonic vibration table or a mechanical wave vibration table, placing the fiber paper in the gel tool, pumping the silica aerogel prepolymer mixture into the fiber paper through a vacuum pump, applying the gravity which is 0.1-0.5 times of the weight of the wet gel paper to the fiber paper after the operation for 5-20min, continuing to operate for 10-30min, closing the vibration table, and standing for 2-24h.
6. The method for preparing the silica nano aerogel heat insulation paper according to claim 5, which is characterized in that: the vibration frequency of the vibration table is 40-80Hz.
7. The method for preparing the silica nano aerogel heat insulation paper according to claim 6, which is characterized in that: the permeable membrane barrier on the surface of the fibrous paper is removed prior to solvent replacement of the wet silica aerogel paper.
8. The method for preparing the silica nano aerogel heat insulation paper according to claim 7, which is characterized in that: the solvent replacement is to place wet silica aerogel paper on tooling partition boards uniformly provided with meshes, apply the gravity of 0.01-0.1 times of the weight of the wet silica aerogel paper on each layer of partition boards, then place the wet silica aerogel paper into the solvent, and replace the wet silica aerogel paper for 4-24 hours at the temperature of 40-65 ℃.
9. The method for preparing the silica nano aerogel thermal insulation paper according to any one of claims 1 to 6, wherein: the solvent replacement is to put wet silica aerogel paper into a solvent and replace the wet silica aerogel paper for 4 to 24 hours at the temperature of 40 to 65 ℃.
10. The method for preparing the silica nano aerogel heat insulation paper according to claim 9, wherein the method comprises the following steps: the hydrophobic modification is to put wet silica aerogel paper subjected to solvent replacement into a hydrophobic agent alcohol solution, and react for 4-24 hours at the temperature of 40-65 ℃ to carry out alkylation in-situ chemical reaction, wherein the hydrophobic agent is one of alkylation reagents such as hexamethyldisilazane, trimethylmethoxysilane, trimethylchlorosilane and the like.
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