CN103213996A - Preparation method of hierarchical-pore silica-based composite aerogel - Google Patents
Preparation method of hierarchical-pore silica-based composite aerogel Download PDFInfo
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Abstract
The invention discloses a preparation method of hierarchical-pore silica-based composite aerogel, which relates to the field of inorganic materials. The preparation method comprises the following steps of: adding a treated mesoporous silica molecular sieve to a precursor solution for obtaining a colloidal sol, then adding a catalyst so that the colloidal sol gels, and finally carrying out supercritical drying/modification and ambient pressure drying to prepare the hierarchical-pore silica-based composite aerogel material. The preparation method has the advantages that (1) the hierarchical-pore silica-based composite aerogel material is prepared by a supercritical drying or ambient pressure drying method; (2) the hierarchical-pore silica-based composite aerogel material prepared by the method provided by the invention is uniform in microstructure and has high strength, good insulation performance, low density and high specific surface area; and (3) the method provided by the invention is simple in preparation technology, mild in reaction conditions and suitable for industrial production.
Description
Technical field
The invention belongs to inorganic thermal insulation material field, be specifically related to a kind of multistage hole silicon dioxide base composite aerogel and preparation method thereof.
Background technology
Aerosil is meant the nanoporous silica cross-linked network structure of assembling formation with the nanometer scale ultrafine particle mutually, contains greater than 90% air with less than 10% solid silica skeleton.The aerosil particular structure makes it have excellent performance: extremely low density and thermal conductivity, very high specific surface area and porosity.In addition, aerosil have also that low-refraction, Young's modulus are little, numerous excellent characteristic such as low acoustic impedance and high adsorption capacity.Therefore, aerosil all has application comparatively widely at basic scientific research, building, military project, aerospace and industrial circle.
But the mesh skeleton structure that aerogel is loose causes its mechanical property relatively poor.Therefore, aerogel is restricted in the application in a lot of fields.In order to improve its mechanical property, often need to add the mixture of fiber-like, but the own consistency of mixture and aerogel is relatively poor, so the zone between mixture and the aerogel is comparatively sparse, cause whole ununiformity; Simultaneously, the adding of fiber has not only improved the density of aerogel greatly, may cause its heat-insulating property and stable on heating reduction significantly simultaneously.
United States Patent (USP) the 5th, 786 discloses for No. 059 and a kind of aerogel particle evenly to be sprayed at two kinds of polymer formation conjugate fiber preparation methods that firmly are connected together.The sample hardness of its preparation is bigger, but under external force can be broken, and promptly the bonding force deficiency of fiber and aerogel does not possess the characteristic that high temperature uses simultaneously yet.Publication number provides a kind of flexible aerogel block body and preparation method thereof for the Chinese patent of CN 102807358 A, its aerogel that makes has flexible preferably, but have a certain distance the relative pure silicon dioxide aerogel of its density, specific surface area and thermal conductivity, and do not possess flame-retarding characteristic.Publication number provides a kind of preparation method of fire-retardant silica aerogel heat insulation composite material for the Chinese patent of CN 102531536 A.The flame-retardant heat insulating effect is better, and still, its preparation method is comparatively complicated, and higher to equipment requirements in the preparation process.Publication number provides a kind of preparation method of heat-resisting alumina-silox aerogel thermal-protective composite material for the Chinese patent of CN 101792299 A, prepared aerogel has the use temperature height, heat-proof quality is good, characteristics such as mechanical strength height, but its preparation process is quite complicated.
In sum, in order to overcome the relatively poor inferior position of mechanical property, using the other materials composite aerogel is a kind of practicable thinking.Yet at present the preparation method of composite aerogel can cause the problems such as inhomogeneous, preparation process complexity of aerogel structure, and may reduce the advantages such as low density, lower thermal conductivity of silica aerogel.Therefore, we have proposed the preparation method of a kind of multistage hole silicon dioxide base composite aerogel: on the one hand, because mesoporous si molecular sieves and nanoporous silica matrices are unbodied silicon-dioxide, therefore its consistency is better, makes composite aerogel density, thermal conductivity with respect to the pure silicon dioxide aerogel too big variation can not take place; On the other hand,, in the aerogel gelation process, not only become the nucleating center, can play certain enhancement to the aerogel skeleton simultaneously because most si molecular sieves are bar-shaped formation.
Summary of the invention
The preparation method of the multistage hole silicon dioxide base composite aerogel of the object of the present invention is to provide that a kind of technology is simple, mild condition, flow process are short, to overcome above-mentioned preparation method's deficiency, and guarantee that the product microtexture that obtains is even, the intensity height, heat-insulating property is good, and density is low and specific surface area is high.
Technical scheme of the present invention is: a) add the mesoporous silica molecular sieve after handling in precursor solution, ultrasonic its homodisperse that makes; B) obtain colloidal sol; C) add catalyzer and make its gel, obtain silica-base composite material; D) prepare multistage hole composite aerogel material through supercritical drying/modification and constant pressure and dry.The multistage hole silicon-dioxide composite aerogel density of material that makes is 0.03 ~ 0.60g/cm
3, porosity is 85 ~ 99.5%, specific surface area is 500 ~ 1000m
2/ g, thermal conductivity are 0.02 ~ 0.05Wm
-1K
-1
Concrete preparation process is:
1. supercritical drying preparation process may further comprise the steps:
1) with deionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst is the ratio uniform mixing of 1:0.5 ~ 5:0.5 ~ 2:0.005 ~ 0.1 with the volume ratio, after stirring, ratio in every 50mL mixing solutions 0.005 ~ 0.1g adds the mesoporous silica molecular sieve powder, after stirring, ultrasonic 10 ~ 30min then leaves standstill 10min ~ 12h under the room temperature;
2) alkaline catalysts of 0.01 ~ 1mol/L that adds the mixing solutions cumulative volume 16% ~ 30% of account for ionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst in the mixing solutions that in step 1), obtains, under room temperature, leave standstill 12 ~ 240h, obtain the gel of homogeneous transparent; Described alkaline catalysts comprises: ammoniacal liquor, Monoethanolamine MEA BASF, a kind of in diethanolamine, the trolamine
3) at room temperature place dehydrated alcohol to carry out replacement(metathesis)reaction above-mentioned gel, replace each 12 ~ 48h 3 ~ 10 times.
4) the block mixture that will obtain places airtight high-temperature high-pressure reaction kettle, is warming up to 260 ~ 300 ℃ with the speed of 5 ~ 20 ℃/min, is incubated after 3 ~ 10 hours, and relief pressure in 1 ~ 5 hour can obtain multistage hole silicon-dioxide composite aerogel material.
Further, described presoma silicon source comprises a kind of in tetraethoxy, the methyl silicate; Described mesoporous silica molecular sieve comprises: one or more among SBA-15, MCM-41, the MCM-48; Described acid catalyst comprises: a kind of in hydrochloric acid, oxalic acid, the citric acid.
Preferably, described presoma silicon source is a tetraethoxy; Described mesoporous silica molecular sieve is SBA-15; Described acid catalyst is a hydrochloric acid; Described alkaline catalysts is an ammoniacal liquor.
2. constant pressure and dry preparation process may further comprise the steps:
1) to the pre-treatment of mesoporous silica molecular sieve, comprise step:
1.1) be that the mixed of 10:7 ~ 3:1 is even with the volume ratio with the hydrogen peroxide of the vitriol oil and 30%.
1.2) place 60 ℃ ~ 100 ℃ above-mentioned solution to soak 1 ~ 5h in the mesoporous silica molecular sieve powder, centrifugation is then used deionized water and absolute ethanol washing 3 ~ 5 times respectively, centrifugation;
1.3) the mesoporous silica molecular sieve powder that obtains placed the dry 6 ~ 12h of 60 ℃ ~ 100 ℃ thermostatic drying chambers after, be cooled to room temperature.
2) with deionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst be the ratio uniform mixing of 1:0.5 ~ 5:0.5 ~ 2:0.005 ~ 0.1 with the volume ratio, after stirring, ratio in every 50mL mixing solutions 0.005 ~ 0.1g adds above-mentioned treated mesoporous silica molecular sieve powder, after stirring, ultrasonic 10 ~ 30min then leaves standstill 10min ~ 12h under the room temperature;
3) to step 2) in add the alkaline catalysts of 0.01 ~ 1mol/L of the mixing solutions cumulative volume 16% ~ 30% of account for ionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst in the mixing solutions that obtains, under room temperature, leave standstill 12 ~ 240h, obtain the gel of homogeneous transparent;
4) above-mentioned gel is placed tensio-active agent, at room temperature carry out replacement(metathesis)reaction, replace each 12 ~ 48h 3 ~ 10 times;
5) gel after will replacing adds modification 24h ~ 72h in surface-modifying agent and the tensio-active agent mixing solutions of mixing solutions cumulative volume 30% ~ 100% that volume is deionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst, and wherein surface-modifying agent and tensio-active agent volume are than being 1:5 ~ 15;
6) above-mentioned gel through modification is placed tensio-active agent, at room temperature carry out replacement(metathesis)reaction, replace each 12 ~ 48h 3 ~ 10 times.
7) the uncovered temperature that places is the dry 72h ~ 240h of thermostat container of room temperature, places 200 ℃ the dry 1 ~ 3h of baking oven afterwards.
Further, the mesoporous silica molecular sieve in the described step 1) comprises: one or more among SBA-15, MCM-41, the MCM-48.
Further, described mesoporous silica molecular sieve is SBA-15.
Further, described presoma silicon source comprises wherein a kind of in tetraethoxy, the methyl silicate; Described acid catalyst comprises: a kind of in hydrochloric acid, oxalic acid, the citric acid; Described alkaline catalysts comprises: ammoniacal liquor, Monoethanolamine MEA BASF, a kind of in diethanolamine, the trolamine; Described tensio-active agent is a kind of in normal hexane, Skellysolve A, methylacetone, the isopropylcarbinol; Described surface-modifying agent is a kind of in methyl trimethoxy oxygen radical siloxane, Union carbide A-162, dimethylchlorosilane, ethoxytrimethylsilane, hexamethyldisilazane, vinyltriethoxysilane, phenyl triethoxysilane, the trimethylchlorosilane.
Preferably, described presoma silicon source is a tetraethoxy; Described acid catalyst is a hydrochloric acid; Described alkaline catalysts is an ammoniacal liquor; Described tensio-active agent is a normal hexane; Described surface-modifying agent is a trimethylchlorosilane.
The invention has the advantages that: 1) made multistage hole silicon dioxide base composite aerogel material by supercritical drying or atmosphere pressure desiccation.2) with the multistage hole silicon dioxide base composite aerogel material of method preparation provided by the invention, the product microtexture is even, the intensity height, and heat-insulating property is good, and density is low and specific surface area is high.3) simple with method preparation technology provided by the invention, reaction conditions is gentle, flow process is short, is fit to suitability for industrialized production.
Specific embodiments
The present invention is further elaborated below in conjunction with specific embodiments.
Case study on implementation 1
A) hydrochloric acid with deionized water, dehydrated alcohol, tetraethoxy and 0.25mol/L is the ratio uniform mixing of 1:1.5:1.5:0.05 with the volume ratio, cumulative volume is 50mL, after stirring, add 0.01g SBA-15 powder, after stirring, ultrasonic 10min leaves standstill 2h and be placed in the room temperature in ultrasonic wave.
B) ammonia soln of adding 10mL 0.5mol/L leaves standstill 48h under room temperature, obtains the gel of homogeneous transparent;
C) at room temperature place dehydrated alcohol to carry out replacement(metathesis)reaction above-mentioned gel, replace 5 times, each 24h;
D) the block mixture that will obtain places airtight high-temperature high-pressure reaction kettle, is warming up to 260 ℃ with the speed of 5 ℃/min, is incubated after 5 hours, and relief pressure in 2 hours can obtain multistage hole silicon-dioxide composite aerogel material.
Case study on implementation 2
A) oxalic acid with deionized water, dehydrated alcohol, tetraethoxy and 0.5mol/L is the ratio uniform mixing of 1:1.5:1.5:0.1 with the volume ratio, cumulative volume is 50mL, after stirring, add 0.01g SBA-15 powder, after stirring, ultrasonic 10min leaves standstill 2h and be placed in the room temperature in ultrasonic wave.
B) ammonia soln of adding 10mL 0.5mol/L leaves standstill 48h under room temperature, obtains the gel of homogeneous transparent;
C) at room temperature place dehydrated alcohol to carry out replacement(metathesis)reaction above-mentioned gel, replace 5 times, each 24h;
D) the block mixture that will obtain places airtight high-temperature high-pressure reaction kettle, is warming up to 260 ℃ with the speed of 5 ℃/min, is incubated after 5 hours, and relief pressure in 2 hours can obtain multistage hole silicon-dioxide composite aerogel material.
Case study on implementation 3
A) be that the mixed of 7:3 is even with the hydrogen peroxide of the vitriol oil and 30% with the volume ratio.
B) the MCM-41 powder is placed 100 ℃ above-mentioned solution soak 3h, (general centrifugal speed is 10000 commentaries on classics/min to obtaining the SiO 2 molecular sieve powder in centrifugation then, about centrifugal 5 ~ 10min), use deionized water and absolute ethanol washing 3 times respectively, centrifugation is to obtaining the SiO 2 molecular sieve powder.
C) the mesoporous silica molecular sieve powder that obtains is placed 80 ℃ of dry 8h of thermostatic drying chamber after, be cooled to room temperature.
D) hydrochloric acid with deionized water, dehydrated alcohol, tetraethoxy and 0.25mol/L is the ratio uniform mixing of 1:1.5:1.5:0.05 with the volume ratio, cumulative volume is 50mL, after stirring, add the above-mentioned treated MCM-41 powder of 0.01g, after stirring, ultrasonic 10min keeps 2h and be placed in the normal temperature in ultrasonic wave.
E) ammonia soln of adding 10mL 0.5mol/L leaves standstill 48h under room temperature, obtains the gel of homogeneous transparent;
F) above-mentioned gel is placed normal hexane, at room temperature carry out replacement(metathesis)reaction, replace 5 times, each 12h;
G) hexane solution (wherein the volume ratio of trimethylchlorosilane is 10%) the modification 24h of adding 30mL trimethylchlorosilane;
H) above-mentioned gel through modification is placed normal hexane, at room temperature carry out replacement(metathesis)reaction, replace 5 times, each 12h;
I) the uncovered temperature that places is the dry 72h of thermostat container of room temperature, places 200 ℃ the dry 2h of baking oven afterwards.
Above case study on implementation only is in order to show and describe the principal character and the ultimate principle of patent of the present invention, and the present invention is not subjected to the restriction of above-mentioned true case, and the claimed scope of the present invention is defined by claims and equivalent thereof.
Claims (10)
1. the preparation method of a multistage hole silicon dioxide base composite aerogel is characterized in that: may further comprise the steps:
1) in the mixing solutions of presoma silicon source, adds mesoporous silica molecular sieve, ultrasonic its homodisperse that makes; 2) at room temperature leave standstill, obtain colloidal sol; 3) add to leave standstill behind the catalyzer and make its gel, obtain silica-base composite material; 4) prepare multistage hole composite aerogel material through supercritical drying/modification and constant pressure and dry.
2. the preparation method of multistage hole according to claim 1 silicon dioxide base composite aerogel is characterized in that: may further comprise the steps:
1) with deionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst is the ratio uniform mixing of 1:0.5 ~ 5:0.5 ~ 2:0.005 ~ 0.1 with the volume ratio, after stirring, ratio in every 50mL mixing solutions 0.005 ~ 0.1g adds the mesoporous silica molecular sieve powder, after stirring, ultrasonic 10 ~ 30min then leaves standstill 10min ~ 12h under the room temperature;
2) alkaline catalysts of 0.01 ~ 1mol/L that adds the mixing solutions cumulative volume 16% ~ 30% of account for ionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst in the mixing solutions that in step 1), obtains, under room temperature, leave standstill 12 ~ 240h, obtain the gel of homogeneous transparent; Described alkaline catalysts comprises: ammoniacal liquor, Monoethanolamine MEA BASF, a kind of in diethanolamine, the trolamine
3) at room temperature place dehydrated alcohol to carry out replacement(metathesis)reaction above-mentioned gel, replace each 12 ~ 48h 3 ~ 10 times;
4) the block mixture that will obtain places airtight high-temperature high-pressure reaction kettle, is warming up to 260 ~ 300 ℃ with the speed of 5 ~ 20 ℃/min, is incubated after 3 ~ 10 hours, and relief pressure in 1 ~ 5 hour can obtain multistage hole silicon-dioxide composite aerogel material.
3. according to the preparation method of multistage hole according to claim 2 silicon dioxide base composite aerogel, it is characterized in that: described presoma silicon source comprises a kind of in tetraethoxy, the methyl silicate; Described mesoporous silica molecular sieve comprises: one or more among SBA-15, MCM-41, the MCM-48; Described acid catalyst comprises: a kind of in hydrochloric acid, oxalic acid, the citric acid.
4. according to the preparation method according to claim 2 or 3 described multistage hole silicon dioxide base composite aerogels, it is characterized in that: described presoma silicon source is a tetraethoxy; Described mesoporous silica molecular sieve is SBA-15; Described acid catalyst is a hydrochloric acid; Described alkaline catalysts is an ammoniacal liquor.
5. the preparation method of multistage hole according to claim 1 silicon dioxide base composite aerogel is characterized in that: may further comprise the steps:
1) to the pre-treatment of mesoporous silica molecular sieve, comprise step:
1.1) be that the mixed of 10:7 ~ 3:1 is even with the volume ratio with the hydrogen peroxide of the vitriol oil and 30%;
1.2) place 60 ℃ ~ 100 ℃ above-mentioned solution to soak 1 ~ 5h in the mesoporous silica molecular sieve powder, centrifugation is then used deionized water and absolute ethanol washing 3 ~ 5 times respectively, centrifugation;
1.3) the mesoporous silica molecular sieve powder that obtains placed the dry 6 ~ 12h of 60 ℃ ~ 100 ℃ thermostatic drying chambers after, be cooled to room temperature;
2) with deionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst be the ratio uniform mixing of 1:0.5 ~ 5:0.5 ~ 2:0.005 ~ 0.1 with the volume ratio, after stirring, ratio in every 50mL mixing solutions 0.005 ~ 0.1g adds above-mentioned treated mesoporous silica molecular sieve powder, after stirring, ultrasonic 10 ~ 30min then leaves standstill 10min ~ 12h under the room temperature;
3) to step 2) in add the alkaline catalysts of 0.01 ~ 1mol/L of the mixing solutions cumulative volume 16% ~ 30% of account for ionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst in the mixing solutions that obtains, under room temperature, leave standstill 12 ~ 240h, obtain the gel of homogeneous transparent;
4) above-mentioned gel is placed tensio-active agent, at room temperature carry out replacement(metathesis)reaction, replace each 12 ~ 48h 3 ~ 10 times;
5) gel after will replacing adds modification 24h ~ 72h in surface-modifying agent and the tensio-active agent mixing solutions of mixing solutions cumulative volume 30% ~ 100% that volume is deionized water, dehydrated alcohol, presoma silicon source and 0.1 ~ 1mol/L acid catalyst, and wherein surface-modifying agent and tensio-active agent volume are than being 1:5 ~ 15;
6) above-mentioned gel through modification is placed tensio-active agent, at room temperature carry out replacement(metathesis)reaction, replace each 12 ~ 48h 3 ~ 10 times;
7) the uncovered temperature that places is the dry 72h ~ 240h of thermostat container of room temperature, places 200 ℃ the dry 1 ~ 3h of baking oven afterwards.
6. the preparation method of multistage hole according to claim 5 silicon dioxide base composite aerogel, it is characterized in that: the mesoporous silica molecular sieve in the described step 1) comprises: one or more among SBA-15, MCM-41, the MCM-48.
7. the preparation method of multistage hole according to claim 6 silicon dioxide base composite aerogel, it is characterized in that: described mesoporous silica molecular sieve is SBA-15.
8. the preparation method of multistage hole according to claim 5 silicon dioxide base composite aerogel is characterized in that: described presoma silicon source comprises wherein a kind of in tetraethoxy, the methyl silicate; Described acid catalyst comprises: a kind of in hydrochloric acid, oxalic acid, the citric acid; Described alkaline catalysts comprises: ammoniacal liquor, Monoethanolamine MEA BASF, a kind of in diethanolamine, the trolamine; Described tensio-active agent is a kind of in normal hexane, Skellysolve A, methylacetone, the isopropylcarbinol; Described surface-modifying agent is a kind of in methyl trimethoxy oxygen radical siloxane, Union carbide A-162, dimethylchlorosilane, ethoxytrimethylsilane, hexamethyldisilazane, vinyltriethoxysilane, phenyl triethoxysilane, the trimethylchlorosilane.
9. according to the preparation method of claim 5 or 8 described multistage hole silicon dioxide base composite aerogels, it is characterized in that: described presoma silicon source is a tetraethoxy; Described acid catalyst is a hydrochloric acid; Described alkaline catalysts is an ammoniacal liquor; Described tensio-active agent is a normal hexane; Described surface-modifying agent is a trimethylchlorosilane.
10. according to the preparation method of claim 1 or 2 or 5 multistage hole silicon dioxide base composite aerogels, it is characterized in that: the described multistage hole silicon-dioxide composite aerogel density of material that makes is 0.03 ~ 0.60g/cm
3, porosity is 85 ~ 99.5%, specific surface area is 500 ~ 1000m
2/ g, thermal conductivity are 0.02 ~ 0.05Wm
-1K
-1
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