CN114874493B - High-density aerogel water-based paste and preparation method thereof - Google Patents

High-density aerogel water-based paste and preparation method thereof Download PDF

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CN114874493B
CN114874493B CN202210776658.6A CN202210776658A CN114874493B CN 114874493 B CN114874493 B CN 114874493B CN 202210776658 A CN202210776658 A CN 202210776658A CN 114874493 B CN114874493 B CN 114874493B
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aerogel
density
paste
powder
water
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CN114874493A (en
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孙光耀
鲁祥凯
云山
朱鹏
张静
王科铮
任天斌
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Shandong Huacui Energy Conservation Technology Co ltd
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Jiangsu Jicui Functional Material Research Institute Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2258Oxides; Hydroxides of metals of tungsten
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B80/00Architectural or constructional elements improving the thermal performance of buildings
    • Y02B80/10Insulation, e.g. vacuum or aerogel insulation

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Thermal Insulation (AREA)

Abstract

The invention relates to the field of heat preservation and insulation materials, in particular to a high-density aerogel water-based paste and a preparation method thereof. The density of the paste is 0.85-1.17 g/cm 3 And the content of aerogel in the paste is 4.6-15 wt%. The aerogel water-based paste material has good density matching with polymer matrixes (such as PE and PP) and the like, does not generate dust in the mixing process, can be better dispersed in the polymer matrixes, greatly improves the heat insulation performance of the material, and solves the problems of difficult mixing with polymers and dust pollution caused by over-low density of aerogel powder.

Description

High-density aerogel water-based paste and preparation method thereof
Technical Field
The invention relates to the field of heat preservation and insulation materials, in particular to an aerogel water-based paste and a preparation method thereof.
Background
The aerogel has a porous network structure, excellent heat insulation performance and light weight, and the density of the silicon dioxide aerogel is only 0.003 g/cm 3 The application performance is improved, however, the dispersibility of the aerogel and the resin matrix is extremely poor due to the difference of the density of the aerogel and other materials (such as the resin matrix), the agglomeration of the aerogel is obvious, and the application difficulty is increased. In addition, organic solvents are often added in the use process of the current aerogel, and the network structure of the aerogel is damaged to a certain extent.
Chinese patent application CN102459079A provides an aerogel composition consisting of an aerogel component, a binder and a surfactant, however, it does not solve the problem of the dispersibility of the aerogel component during use. In the preparation method of the heat-insulating composite material in chinese patent CN104496399B, the silica aerogel powder is directly added into the mixed solution, especially when the content of the added silica aerogel is too much, the non-uniformity of the mixing is inevitably increased, and more operation time is needed to obtain a material with good uniformity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides, in a first aspect, a high-density aerogel aqueous paste, wherein the density of the paste is 0.85-1.17 g/cm 3 And the aerogel content in the paste is 4.6-15 wt%.
Preferably, the preparation raw materials comprise aerogel powder, water and an inorganic filler in a weight ratio of x: y: z, wherein x: y = 0.30-0.50, and x: z = 0.06-0.32.
Preferably, the raw materials for preparing the high-density aerogel water-based paste further comprise a dispersing agent, and the weight of the dispersing agent is 0.3-0.8% of the total weight of the raw materials except for the dispersing agent.
The dispersant in the present application is not particularly limited, and may be one or more selected from the group consisting of anionic, cationic, nonionic, amphoteric and electroneutral types, and specifically includes one or more selected from the group consisting of ammonium salt type dispersants, quaternary ammonium salt type dispersants, heterocyclic type dispersants, xanthate type dispersants, carboxylate, sulfonate, sulfate, phosphate and the like.
Preferably, the aerogel powder satisfies at least one of the following conditions:
(a) the average particle size is 1 to 15 μm;
(b) the tap density is 0.1-0.2 g/cm 3 (ii) a The tap density is preferably 0.15 g/cm 3
(c) The thermal conductivity at 25 ℃ is less than 0.024W/(m.K).
Preferably, the aerogel powder is hydrophobic aerogel powder.
Preferably, the hydrophobic aerogel powder is selected from one or more of carbon aerogel, silica aerogel, graphene oxide aerogel, fullerene aerogel, fiber/silica aerogel, alumina aerogel, titanium oxide aerogel, copper oxide aerogel, zirconium oxide aerogel and polymer aerogel. The hydrophobic aerogel powder can prevent water from entering the pore channel, and huge capillary force is generated in the pore channel when the water is prevented from volatilizing, so that the aerogel structure is damaged, collapse is caused, and the heat insulation performance of the aerogel is lost. However, the hydrophobic aerogel is difficult to disperse in water sufficiently due to its water-repellent property, and cannot sufficiently exert heat-insulating and moisture-retaining effects in the system; the applicant finds that the problem can be effectively solved by adopting 0.3-0.8% of dispersing agent through a large amount of researches, so that the hydrophobic aerogel powder can fully play a role in a formula system, and the heat-insulating board is further endowed with a lower heat conductivity coefficient.
Preferably, the inorganic filler is selected from one or more of titanium oxide, vanadium oxide, calcium oxide, zirconium oxide, tungsten oxide, potassium hexatitanate, sodium titanate, and magnesium titanate. When the inorganic filler is potassium hexatitanate, the tap density of the aerogel water-based paste is improved, the heat conductivity coefficient of the potassium hexatitanate at high temperature is reduced, the prepared master batch has stable heat insulation performance, and the quality is guaranteed.
In one embodiment, the inorganic filler has a density of 3.3 to 7.3g/cm 3 And can be exemplified by 3.3g/cm 3 ,4.17g/cm 3 ,5.9g/cm 3 ,7.27g/cm 3 And the like.
The second aspect of the present invention provides a method for preparing the high-density aerogel aqueous paste, comprising the following steps: mixing aerogel powder, water, a dispersing agent and an inorganic filler at the rotation speed of 1000-5000rpm for 10-180 min.
The third aspect of the invention provides an application of the high-density aerogel water-based paste as a heat preservation and insulation auxiliary agent in the processing of high polymer materials.
Compared with the prior art, the invention has the following beneficial effects:
1. because the density of the aerogel water-based paste is far greater than that of the aerogel powder, the density matching performance is better when the aerogel water-based paste is compounded with other materials (such as a resin matrix), the problem of poor dispersibility caused by too low density of the aerogel can be better solved, and the materials can be more uniformly mixed and dispersed.
2. By adopting the aerogel water-based paste material, the problems of dust pollution, difficult blanking and the like in the mixing and granulating process of aerogel powder and a plastic matrix can be solved, the environment is protected, and the operation is simpler and more convenient.
3. The invention does not relate to organic solvents, is safe and environment-friendly, does not damage the pore structure of the aerogel, and can exert the heat preservation and insulation functions to the maximum extent.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Example 1
An aerogel aqueous paste consisting of 30g of silica aerogel powder, 100g of water, 260g of an inorganic filler (the weight ratio of silica aerogel powder to water is x: y =0.30, the weight ratio of silica aerogel powder to inorganic filler is x: z = 0.12), and 1.95g of a dispersant tego 750W; the amount of the dispersant was 0.5wt% of the total amount of the materials other than the above.
Wherein the particle diameter of the silicon dioxide aerogel powder is 1 mu m, and the tap density is 0.1g/cm 3 The thermal conductivity coefficient is 0.018W/(m.K); the inorganic filler is titanium oxide with the density of 4.26g/cm 3
The preparation method of the aerogel water-based paste comprises the following steps: mixing silicon dioxide aerogel powder, water, titanium oxide and a dispersant tego 750W, and mixing at 2000rpm for 5min to obtain the aerogel with the content of 7.65wt% and the density of 0.85g/cm 3 An aerogel aqueous paste.
Example 2
The raw materials are adopted and are consistent with those in the example 1, and the weight of water is 100 g; except that the weight of the inorganic filler was 350 g such that x: y =0.3 and x: z =0.09, and the amount of the dispersant was 2.40g (weight was 0.5wt% of the total amount of the materials except for this). The density of the prepared aerogel water-based paste is 1.00g/cm 3 The aerogel content was 6.22 wt%.
Example 3
The raw materials are adopted and are consistent with those in the example 1, and the weight of water is 100 g; except that the weight of the inorganic filler is 465 g, so that x: y =0.3, x: z =0.07, andthe amount of the dispersant was 2.98g (weight: 0.5wt% of the total amount of the materials except for that). The density of the prepared aerogel water-based paste is 1.17g/cm 3 The aerogel content was 5.02 wt%.
Examples 4 to 12
The raw material and product information used are shown in table 1.
TABLE 1
Figure DEST_PATH_IMAGE001
Comparative example 1
An aerogel aqueous paste, the specific implementation manner is the same as that of example 1; the difference is that the amount of the inorganic filler is 0 (the amount of the dispersant is 0.65 g), the content of the prepared aerogel is 22.96wt percent, and the density is 0.33g/cm 3 An aerogel aqueous paste.
Comparative example 2
An aerogel aqueous paste, the specific implementation manner is the same as that of example 1; the difference is that the raw materials are silica aerogel powder with the weight of 4.85g, water with the weight of 100g (the weight ratio of the aerogel powder to the water is x: y = 0.05), the using amount of the inorganic filler is 0, and 0.52g of dispersant tego 750W, the aerogel content is 4.6wt%, and the density is 0.71g/cm 3 An aerogel aqueous paste.
Comparative example 3
An aerogel aqueous paste, the specific implementation manner is the same as that of example 1; the difference is that the raw materials are silicon dioxide aerogel powder with the weight of 17.75g, water with the weight ratio of the aerogel powder to the water of x: y =0.18, 0 amount of inorganic filler and 0.52g of dispersant tego 750W, the aerogel content is 15wt%, and the density is 0.42/cm 3 An aerogel aqueous paste.
Comparative example 1 compared with example 1, the aerogel content of the comparative example 1 was more than 20% and the density was 0.33g/cm without adding the inorganic filler 3 It only meets the requirement of high content of aerogel, but does not meet the requirement of high density. Comparative examples 2 and 3 compared with example 1, the density ratio of the inorganic filler is 0.85g/cm 3 Low. In summary of the comparative example, theUnder the condition of using pure aerogel powder or not adding inorganic filler, the aerogel content is required to be 4.6-15 wt%, the requirement of high density is difficult to achieve, and only the high-density paste can be mixed with the high polymer material to be dispersed more uniformly, so that the high heat insulation performance is achieved.
Application example 1
The paste of example 1 (0.85 g/cm) was used 3 ) With a plastic resin matrix PE (density of 0.9 g/cm) 3 ) After mixing at a weight ratio of 73.4:26.6, continuously melting and mixing for 15min at 120 ℃, and casting and molding to obtain the heat-insulating plate (the aerogel content is 6.91%).
The obtained aerogel-containing PE insulation board is tested, and the thermal conductivity coefficient is 0.041W/(m.K), the compressive strength is 25.5 MPa, and the bending strength is 10.2 MPa.
Application examples 2 to 4
The aerogel paste of example 8 (p =1.00 g/cm) was used 3 ) Mixing the aerogel-containing PE insulation board with a plastic resin matrix according to a weight ratio of 50:50, continuously melting and mixing for 15min at 120 ℃, casting and molding to obtain the aerogel-containing PE insulation board (the aerogel content is 6.91%), and testing the obtained aerogel-containing PE insulation board.
The results of the tests on the starting materials and products used in application examples 2 to 4 are shown in Table 2.
TABLE 2
Figure 769009DEST_PATH_IMAGE002
Application comparative example 1
Aerogel powder (tap density of 0.2 g/cm) is directly adopted 3 ) With a plastic resin matrix PE (density of 0.9 g/cm) 3 ) Mixing the materials according to the weight ratio of 6.91:93.09, then continuously melting and mixing the materials for 15min at the temperature of 120 ℃, and casting and molding the materials into the heat-preservation plate (the aerogel content is 6.91%).
The aerogel powder is directly added to be mixed with the resin in a melting way, because the density of the aerogel powder is too low, the mixture of the aerogel powder and the resin matrix is very poor, the aerogel powder is positioned at the upper part of the resin, the uniformity of the texture of the heat-insulating plate obtained by casting is very poor, and the heat conductivity coefficient is higher when a heat conductivity coefficient test is carried out, and the average data is 0.25W/(m.K).
Comparative application example 2
The aqueous aerogel paste obtained in comparative example 1 (density 0.33 g/cm) was used 3 ) With a plastic resin matrix PE (density of 0.9 g/cm) 3 ) Mixing at a weight ratio of 24.4:75.6, continuously melting and mixing at 120 ℃ for 15min, and casting to form the heat-insulating plate (the aerogel content is 6.91%).
The density difference between the aerogel water-based paste and the resin matrix is larger, the dispersion effect of the aerogel water-based paste is better than that of aerogel powder, but the prepared insulation board is poorer in texture uniformity and has a partial agglomeration phenomenon unlike a high-density aerogel paste. The obtained aerogel-containing PE insulation board is tested, and the average thermal conductivity coefficient is 0.18W/(m.K).
Comparative application example 3
An aerogel water-based paste, the specific implementation mode is the same as that of application example 1; the difference is that the aerogel powder adopts hydrophilic aerogel powder. The prepared aerogel has the content of 7.65wt percent and the density of 0.85g/cm 3 The aerogel aqueous paste is cast and molded into a PE thermal insulation board (aerogel content is 6.91%).
The obtained aerogel-containing PE insulation board is tested, and the average thermal conductivity coefficient is 0.36W/(m.K). This is because when hydrophilic aerogel powder is used to prepare the paste, water enters into the aerogel micropores and generates huge capillary force when volatilizing, which destroys the aerogel structure and collapses the aerogel structure, thereby losing high-efficiency heat insulation performance, and the measured heat conductivity coefficient is not much different from that of the PE pure master batch.
Application comparative example 4
An aerogel water-based paste, the specific implementation mode is the same as that of application example 1; the difference is that the density of the aerogel powder is 0.2g/cm 3 The inorganic filler is tungsten oxide and the density is 7.27g/cm 3 . The prepared aerogel has the content of 7.65 weight percent and the density of 1.36g/cm 3 The aerogel aqueous paste is cast and molded into a PE thermal insulation board (aerogel content is 6.91%).
Compared with application example 1, although the content of aerogel powder in the paste and the insulation board is the same, the density is higher, so that the dispersion effect is not good when the paste and the insulation board are mixed with PE (polyethylene), and agglomeration is not known to exist in part of the paste and the insulation board, so that the performance of the insulation board is reduced. Tests show that the average thermal conductivity is 0.11W/(m.K), the compressive strength is 18.7 MPa, and the bending strength is 8.6 MPa, which are all inferior to those of the application example 1.
Comparative application example 5
An aerogel water-based paste, the specific implementation mode is the same as that of application example 1; except that x: y =0.6, x: z =0.5, and the amount of the dispersant was 1.4g (weight was 0.5wt% of the total amount of the materials except for that). The density of the prepared aerogel water-based paste is 0.38g/cm 3 The aerogel content was 21.32 wt%.
Mixing the obtained paste (0.65 g/cm) 3 ) With a plastic resin matrix PE (density of 0.9 g/cm) 3 ) The ratio of the weight of the mixed solution to the weight of the mixed solution is 29.1: 70.9, then continuously melting and mixing for 15min at 120 ℃, and casting and molding to obtain the heat-insulating board (aerogel content is 6.91%).
When the aerogel water-based paste is mixed with the resin matrix PE, the whole distribution is poor, more agglomeration phenomenon occurs, and the prepared insulation board is uneven in texture. The obtained aerogel-containing PE insulation board is tested, and the average thermal conductivity coefficient is 0.14W/(m.K), the compressive strength is 13.7MPa, the bending strength is 5.5MPa, and the thermal conductivity is also poorer than that of the application example 1.
Compared with the application example 2, the aerogel powder and the resin matrix are mixed and melted to prepare the aerogel-containing insulation board only in the application comparative example 1, the aerogel powder is located at the upper part of the resin due to too low density of the aerogel powder, the prepared insulation board is uneven in texture, the heat conductivity coefficient is 0.25W/(m.K), and the aerogel-containing insulation board with the uniform texture in the application example 2 (the heat conductivity coefficient is 0.042W/(m.K)) is poor in effect. Compared with the application example 2, the aerogel paste with low density in the comparative example 1 and the resin matrix are mixed and melted to prepare the aerogel-containing insulation board, the dispersion effect is poor, the prepared insulation board has partial agglomeration, the heat conductivity coefficient is 0.18W/(m.K), and the effect is also poor compared with that of the insulation board obtained in the application example 2. Therefore, the high-solid-content and high-density aqueous aerogel paste obtained by the invention has a very good application effect in the processing of high polymer materials. Application comparative example 3 adopts hydrophilic aerogel powder to replace hydrophobic aerogel powder, and although the hydrophilic aerogel powder has good dispersibility in the water-based paste, the prepared insulation board has poor effect because the aerogel structure is damaged. The application comparative example 4 is to prepare the heat insulation board with the same aerogel content by adopting the paste with the same aerogel content and different densities as those of the application example 1, and the paste with the same aerogel content and different densities cannot be uniformly distributed due to higher density, so that the heat conductivity coefficient of the application comparative example 4 is slightly higher, and the compression resistance and the bending resistance are relatively poorer. The application comparative example 5 adopts a formula which is not the formula of the invention to prepare the heat-insulating board with the aerogel content same as that of the application example 1, the problems same as the application comparative example 4 occur, and the heat-insulating performance, the compression resistance and the bending resistance are not the same as those of the application example 1.
The utility model provides an aerogel aqueous paste material, through adding suitable inorganic filler, and control the weight ratio of aerogel powder and inorganic filler, not only make aerogel aqueous paste material density far away be greater than the density of aerogel powder, make the aerogel be convenient for the application of low reaches product better, possess better density suitability with various materials commonly used (like the resin base member), the problem of unable even compounding and dispersion has been avoided, probably because aerogel and inorganic filler's weight ratio control is within this scope simultaneously, not only the reunion nature between inorganic filler and between the aerogel powder has been solved simultaneously, make good dispersion and contact nature between the aerogel powder on the contrary, reach the thermal-insulated purpose of keeping warm. In addition, suitable inorganic filler mentioned in this application refers to a substance having a certain infrared radiation function, and reduces the problem of the performance reduction of the aerogel paste caused by the use of the filler.

Claims (6)

1. The high-density aerogel water-based paste is characterized by having a density of 0.85-1.17 g/cm 3 The content of aerogel in the paste is 4.6-15 wt%; the preparation raw materials of the paste comprise aerogel powder, water and inorganic filler in a weight ratio of x to y to z, wherein x to y = 0.3-0.5, and x to z = 0.06-0.32;
the preparation raw materials also comprise a dispersing agent, and the weight of the dispersing agent is 0.3-0.8% of the total weight of the preparation raw materials except the dispersing agent;
the aerogel powder is hydrophobic aerogel powder;
the inorganic filler is selected from one or more of titanium oxide, vanadium oxide, calcium oxide, zirconium oxide, tungsten oxide, potassium hexatitanate, sodium titanate and magnesium titanate.
2. A high density aerogel aqueous paste according to claim 1, wherein the aerogel powder satisfies at least one of the following conditions:
(a) the average particle size is 1 to 15 μm;
(b) the tap density is 0.1-0.2 g/cm 3
(c) The thermal conductivity coefficient is less than 0.024W/(mK) at 25 ℃.
3. The high density aerogel aqueous paste of claim 1, wherein the aerogel powder is selected from one or more of carbon aerogel, silica aerogel, graphene oxide aerogel, fullerene aerogel, fiber/silica aerogel, alumina aerogel, titania aerogel, copper oxide aerogel, zirconia aerogel, polymer aerogel.
4. The high density aerogel aqueous paste of claim 3, wherein the inorganic filler has a density of 3.3 to 7.3g/cm 3
5. A method of preparing a high density aerogel aqueous paste according to any of claims 1 to 4, comprising the steps of: mixing aerogel powder, water, a dispersing agent and an inorganic filler at the rotation speed of 1000-5000rpm for 10-180 min.
6. Use of a high density aerogel aqueous paste according to any of claims 1-4 as a thermal insulation aid in the processing of polymeric materials.
CN202210776658.6A 2022-07-04 2022-07-04 High-density aerogel water-based paste and preparation method thereof Active CN114874493B (en)

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