CN109988339A - With mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof - Google Patents

With mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof Download PDF

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CN109988339A
CN109988339A CN201810006069.3A CN201810006069A CN109988339A CN 109988339 A CN109988339 A CN 109988339A CN 201810006069 A CN201810006069 A CN 201810006069A CN 109988339 A CN109988339 A CN 109988339A
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montmorillonite
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weight
carbon nanotube
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李洪彦
付永强
刘洪丽
魏冬青
李海明
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Tianjin Chengjian University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
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Abstract

The present invention provides the mesh carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof with mesoporous and micropore, after preparing the wet gel and montmorillonite wet gel that carbon nanotube carries deca-BDE respectively, after the two is mixed with ammonium polyphosphate solution, mesh carbon nanotube-montmorillonite Composite aerogel material with mesoporous and micropore is made.It uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, using the meso-hole structure of aeroge and the microcellular structure of fiber, load deca-BDE and ammonium polyphosphate respectively, different characteristics fire retardant is combined, realize cooperative flame retardant effect.

Description

With mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material and Preparation method
Technical field
The present invention relates to technical field of nano material, more specifically to a kind of with mesoporous and micropore reticulated carbon Nanotube-montmorillonite Composite aerogel material and preparation method thereof.
Background technique
Montmorillonite (MMT) is a kind of electronegative silicate lamella in surface by nano thickness (about 1nm) by interlayer Electrostatic interaction and the earthy mineral for being packed together composition.Structure cell in its crystal structure is by folder among two layers of oxygen-octahedron One layer of alumina octahedral is constituted, and belongs to 2:1 type phyllosilicate.(the organically-modified research of Xie Youli, Zhang Meng, Zhou Yonghong montmorillonite Be in progress [J] chemical industry progress, 2012, (04): 844-851.) structure cell in its crystal structure is by among two layers of oxygen-octahedron It presss from both sides one layer of alumina octahedral to constitute, belongs to 2:1 type phyllosilicate.This special crystal structure assigns the unique property of montmorillonite Matter, such as surface polarity is big, cation exchange capacity (CEC) is strong, interlayer surface is aqueous.
The thickness of every layer of montmorillonite is about 1nm, and respectively about 100nm, interlamellar spacing are about 1nm or so to length and width.Due to montmorillonite Part trivalent aluminium makes layer inner surface have negative electrical charge by divalent magnesium isomorphous substitution on alumina octahedral, and superfluous negative electrical charge passes through The cation of Inter layer adsorption compensates, they are easy to swap with inorganic or organic cation.(Zhou Chunhui, Cai Ye, sieve tin It is flat, Ge Zhonghua, Li little Nian, the alkylation performance and structural research [J] high of Liu Huayan montmorillonite load type solid acid catalyst School chemical engineering journal, 2003, (01): 96-100.) montmorillonite after organic cation exchange is in lipophilicity, and interlayer Distance increases.Organic modification montmonrillonite can be removed further during with monomer or Mixing of Polymer Melt as nanometer ruler The frame sheet of degree, it is evenly dispersed in a polymer matrix, to form nanocomposite.
Montmorillonite-based nano pipe has unique nanostructure, is a kind of natural nano-material having a extensive future.And montmorillonite Nanotube is widely distributed, cheap, nontoxic.Montmorillonite because of its unique nanostructure, have the advantage that firstly, It is from a wealth of sources, it is cheap；Montmorillonite is a kind of natural clay mineral, contain it is abundant, it is widely distributed and exploitation be easier to.Secondly, With good biocompatibility；Montmorillonite-based nano pipe self-assembling formation, nontoxic, biocompatibility is preferable.In addition, active hydroxyl Base is contained in montmorillonite surface and interlayer, conducive to montmorillonite modification and further apply.Along with itself has nanometer ruler The features such as spending, montmorillonite have obtained extensive concern and research in recent years.
The application field of montmorillonite-based nano pipe is extensive.In ceramic material, composite material, slow-release material, catalyst carrier, mould Plate, adsorption applications etc. have a large amount of application.Because montmorillonite-based nano pipe is a kind of clay mine, it can be used for ceramic system Make, this belongs to traditional application field of montmorillonite.Montmorillonite has the function of fiber reinforcement, is the ideal for preparing ultra-thin fine ceramics Raw material.In recent years, the research of galapectite/polymer composites and its performance was becoming increasingly popular.Montmorillonite can be Preferably disperse in most polymer composite material, mechanical property, thermal stability, anti-flammability and the knot of polymer can be effectively improved Brilliant performance, having biggish advantage compared with other conventional fillers, (Ma Jianzhong, Chen Xinjiang, Chu Yun, the remote montmorillonite-based nano of poplar ancestor are multiple Preparation and application study [J] Chinese leather of condensation material, 2002, (21): 15-20.).Montmorillonite has unique texture, environment The features such as friendly, cheap and easy to get, can prepare the material with new structure and performance using its design feature and characterization of adsorption, It is widely used in field of nanocomposite materials.
Summary of the invention
The present invention overcomes deficiencies in the prior art, provide a kind of with mesoporous and micropore mesh carbon nanotube- Montmorillonite Composite aerogel material and preparation method thereof uses the doughnut with microcellular structure for raw material, builds three-dimensional gas Gel network loads different flame retardant respectively, different characteristics is hindered using the meso-hole structure of aeroge and the microcellular structure of fiber It fires agent to combine, realizes cooperative flame retardant effect.
The purpose of the present invention is achieved by following technical proposals.
With mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof, under State step progress:
Step 1,0.6-12 parts by weight lauryl sodium sulfate (SDS), 0.01-18 parts by weight deca-BDE is taken to be added In 100 parts by weight water, after sonic oscillation is uniform, the carbon nanotube of 0.8-12 parts by weight is added thereto, after ultrasonic disperse is uniform, Vacuum is kept after vacuumizing, is then restored to normal pressure, is repeated vacuum step three times, is obtained the wet gel of step 1；
Step 2, by after 0.09-12 parts by weight montmorillonite drying, dispersed with the montmorillonite that solvent is configured to 0.06-24wt% Liquid, montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the wet gel of step 2；
Step 3, by the wet gel of 0.7-32 parts by weight step 1, the wet gel of 0.8-30 parts by weight step 2,0.3-16 weight It measures the ammonium polyphosphate solution that part mass fraction is 0.05-18wt% to mix, stirs evenly after being then sonicated centrifugation, produced Object, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium at 10-300 DEG C of temperature and air pressure 1-20MPa Supercritical drying at least 1h is carried out, can obtain that there is mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material.
In step 1,1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight deca-BDE are added In water, after sonic oscillation 2-48h, the carbon nanotube of 1-10 parts by weight is added thereto, after ultrasonic disperse 1-24h, after vacuumizing Keep 0.5-2h.
In step 2, the montmorillonite of 0.1-10 parts by weight is dried to 5-20h at 60-180 DEG C, is configured to 0.1- with solvent Montmorillonite dispersions are stirred 4- at 5-35 DEG C with the speed mechanical of 150-400r/min by the montmorillonite dispersions of 20wt% 10h, then the ultrasonic treatment 6-15h with 50-300W power.
In step 3,1-30 parts by weight of carbon nanotubes is carried into medicine wet gel, 1-30 parts by weight montmorillonite wet gel, 0.5- The ammonium polyphosphate solution that 15 parts by weight mass fractions are 0.05-15wt% mixes, and 10-25h is stirred at 5-35 DEG C, is ultrasonically treated 6-15h is finally centrifuged 1-8h under 1000-3500rpm revolving speed.
In step 3, the supercritical drying time is 2-4h, preferably 3h.
The deca-BDE being added in step 1 is dispersed in carbon nanotube hollow structure, and carbon nanotube hollow structure is Microcellular structure is provided with mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material, deca-BDE is born It is loaded in carbon nanotube, forms tridimensional network between carbon nanotube, the montmorillonite being added in step 2 is successfully configured to network Pore structure, above-mentioned tridimensional network and carbon nanotube are successfully configured to network pore structure and together form three-dimensional network hole Gap structure, above-mentioned three-dimensional network pore structure are with mesoporous and micropore mesh carbon nanotube-montmorillonite Composite airsetting glue material Material provides meso-hole structure, while ammonium polyphosphate being supported in meso-hole structure.
Using scientific and technological (Beijing) the Co., Ltd 3H-2000PS1 type static volumetric method specific surface area of Bei Shide instrument and aperture The N of the tester analysis composite material that according to the present invention prepared by the method2Adsorption-desorption curve, such as Fig. 1.It can be with from figure Find out, the N of the material2Adsorption-desorption curve is the IV class isothermal curve of H1 type hysteresis loop in IUPAC classification, i.e., by mesoporous knot Structure generates.Illustrate that material itself has the pore structure of meso-scale.There is vertical ascent trend from the distribution of low pressure endpoint, can see Sample interior is as caused by absorption potential strong inside micropore there are more micropore out.By nitrogen adsorption desorption isotherm data, The sample specific surface area can reach 603.32m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, surveys through multiple groups The average specific surface area for measuring material is 601-604m2g-1。
By N2Data in adsorption-desorption curve are substituted into correlation values, can be arranged by BJH formula and Kelvin equation Obtain the accounting equation r in aperturek=-0.971/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.347 [- 5/ ln(p/p0)] ^ (1/3), can obtain effective aperture is r=rk+ t, therefore aperture is the function influenced by relative pressure, so may be used In the hope of the aperture under different relative pressures, it can calculate and acquire in material that there are two aperture points to be distributed, Yi Zhongwei 10.27nm, another kind are 20.61 μm, are measured through multiple groups, and nanoscale hole is average up to 10-11nm, and micro-meter scale hole is flat Up to 19-21 μm.It can be seen that material exists simultaneously nanoscale and micro-meter scale hole.
Using the Nanosem430 field emission scanning electron microscope of Dutch Philips to the method for the invention system of utilization The microscopic appearance of standby composite material is observed, as shown in Figure 2.It can be seen from the figure that montmorillonite layer is successfully configured to Network pore structure, aperture size is in mesoporous scale.It is overlapped to form three-dimensional netted carbon nanotube and is uniformly dispersed in montmorillonite three It ties up in network pore, realizes the building of dual load system.
Detailed description of the invention
Fig. 1 is that have mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material N2Adsorption-desorption is bent Line；
Fig. 2 is that have mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material electromicroscopic photograph.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1
Take 1g lauryl sodium sulfate (SDS), 10g deca-BDE be added 100g water in, sonic oscillation for 24 hours after, be added The carbon nanotube of 5g, ultrasonic disperse 5h, obtains dispersion liquid；0.5h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to often Pressure repeats vacuum step three times, obtains carbon nanotube carrier wet gel；10h is dried into 0.5g montmorillonite at 78 DEG C, then is used Solvent is configured to the montmorillonite dispersions that mass fraction is 6wt%；By montmorillonite dispersions with the speed of 190r/min at 26 DEG C Mechanical stirring 5h is spent, then with the ultrasonic treatment 11h of 150W power, obtains montmorillonite wet gel；12g carbon nanotube carrier is wet solidifying Glue, 21g montmorillonite wet gel, the ammonium polyphosphate solution that 0.5g mass fraction is 5.9wt% mix, and 19h is stirred at 8 DEG C, then It is ultrasonically treated 6h, 8h is finally centrifuged under 1200rpm revolving speed, obtains solution, then place the product in CO2Supercritical, high pressure extraction In device, with CO2Supercritical drying 3h is carried out at 150 DEG C of temperature and air pressure 10MPa for medium, and carbon nanotube/illiteracy can be obtained The de- multiple dimensioned carrier aeroge of soil.
Embodiment 2
It takes 5g lauryl sodium sulfate (SDS), 5g deca-BDE to be added in 100g water, after sonic oscillation 2h, 3g is added Carbon nanotube, ultrasonic disperse 1h obtains dispersion liquid；2h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to normal pressure, weight Multiple vacuum step three times, obtains carbon nanotube carrier wet gel；7h is dried into 5g montmorillonite at 155 DEG C, then is matched with solvent It is set to the montmorillonite dispersions that mass fraction is 2wt%；By montmorillonite dispersions with the speed mechanical of 400r/min at 35 DEG C 4h is stirred, then with the ultrasonic treatment 9h of 288W power, obtains montmorillonite wet gel；By 13g carbon nanotube carrier wet gel, 10g Montmorillonite wet gel, the ammonium polyphosphate solution that 12g mass fraction is 3wt% mix, and stir 11h at 30 DEG C, are then sonicated 7h is finally centrifuged 6h under 2500rpm revolving speed, obtains solution, then place the product in CO2In supercritical high-pressure extraction device, With CO2Supercritical drying 3h is carried out at 300 DEG C of temperature and air pressure 9MPa for medium, and the more rulers of carbon nanotube/montmorillonite can be obtained Spend carrier aeroge.
Embodiment 3
It takes 3g lauryl sodium sulfate (SDS), 15g deca-BDE to be added in 100g water, after sonic oscillation 16h, is added The carbon nanotube of 6g, ultrasonic disperse 19h, obtains dispersion liquid；1.5h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to often Pressure repeats vacuum step three times, obtains carbon nanotube carrier wet gel；By 3g montmorillonite at 180 DEG C dry 5h, then with molten Agent is configured to the montmorillonite dispersions that mass fraction is 13wt%；By montmorillonite dispersions with the speed of 150r/min at 12 DEG C Mechanical stirring 6h, then with the ultrasonic treatment 8h of 300W power, obtain montmorillonite wet gel；By 25g carbon nanotube carrier wet gel, 30g montmorillonite wet gel, the ammonium polyphosphate solution that 15g mass fraction is 0.05wt% mix, and 25h are stirred at 21 DEG C, then surpass Sonication 8h is finally centrifuged 5h under 3500rpm revolving speed, obtains solution, then place the product in CO2Supercritical, high pressure extraction dress In setting, with CO2Supercritical drying 3h is carried out at 220 DEG C of temperature and air pressure 20MPa for medium, and it is de- that carbon nanotube/illiteracy can be obtained The multiple dimensioned carrier aeroge of soil.
Embodiment 4
It takes 10g lauryl sodium sulfate (SDS), 0.05g deca-BDE to be added in 100g water, after sonic oscillation 5h, adds Enter the carbon nanotube of 1g, ultrasonic disperse for 24 hours, obtains dispersion liquid；1h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to often Pressure repeats vacuum step three times, obtains carbon nanotube carrier wet gel；By 8g montmorillonite at 95 DEG C dry 19h, then with molten Agent is configured to the montmorillonite dispersions that mass fraction is 0.6wt%；By montmorillonite dispersions at 5 DEG C with the speed of 330r/min Mechanical stirring 8h, then with the ultrasonic treatment 6h of 50W power, obtain montmorillonite wet gel；By 30g carbon nanotube carrier wet gel, 29g montmorillonite wet gel, the ammonium polyphosphate solution that 13g mass fraction is 9.3wt% mix, and 10h, then ultrasound are stirred at 35 DEG C 10h is handled, 4h is finally centrifuged under 1900rpm revolving speed, obtains solution, then place the product in CO2Supercritical, high pressure extraction dress In setting, with CO2Supercritical drying 3h is carried out at 188 DEG C of temperature and air pressure 12MPa for medium, and it is de- that carbon nanotube/illiteracy can be obtained The multiple dimensioned carrier aeroge of soil.
Embodiment 5
It takes 6g lauryl sodium sulfate (SDS), 3.5g deca-BDE to be added in 100g water, after sonic oscillation 48h, is added The carbon nanotube of 7g, ultrasonic disperse 10h, obtains dispersion liquid；2h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to often Pressure repeats vacuum step three times, obtains carbon nanotube carrier wet gel；By 7g montmorillonite at 87 DEG C dry 15h, then with molten Agent is configured to the montmorillonite dispersions that mass fraction is 8wt%；By montmorillonite dispersions with the speed machine of 290r/min at 9 DEG C Tool stirs 10h, then with the ultrasonic treatment 15h of 122W power, obtains montmorillonite wet gel；By 1g carbon nanotube carrier wet gel, 16g montmorillonite wet gel, the ammonium polyphosphate solution that 6g mass fraction is 0.9wt% mix, and are stirred at 23h, then ultrasound at 5 DEG C 12h is managed, 2h is finally centrifuged under 3000rpm revolving speed, obtains solution, then place the product in CO2Supercritical high-pressure extraction device In, with CO2Supercritical drying 3h is carried out at 10 DEG C of temperature and air pressure 1MPa for medium, and it is more that carbon nanotube/montmorillonite can be obtained Scale carrier aeroge.
Embodiment 6
It takes 9g lauryl sodium sulfate (SDS), 9.7g deca-BDE to be added in 100g water, after sonic oscillation 31h, is added The carbon nanotube of 10g, ultrasonic disperse 8h, obtains dispersion liquid；0.5h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to often Pressure repeats vacuum step three times, obtains carbon nanotube carrier wet gel；20h is dried into 5.6g montmorillonite at 133 DEG C, then The montmorillonite dispersions that mass fraction is 0.1wt% are configured to solvent；By montmorillonite dispersions with 365r/min at 20 DEG C Speed mechanical stir 9h, then with the ultrasonic treatment 13h of 92W power, obtain montmorillonite wet gel；9g carbon nanotube carrier is wet Gel, 6g montmorillonite wet gel, the ammonium polyphosphate solution that 4.6g mass fraction is 15wt% mix, and stir 20h at 12.5 DEG C, It is then sonicated 15h, 1h is finally centrifuged under 1000rpm revolving speed, obtains solution, then place the product in CO2Supercritical, high pressure In extraction equipment, with CO2Supercritical drying 3h is carried out at 24 DEG C of temperature and air pressure 5MPa for medium, can be obtained carbon nanotube/ The multiple dimensioned carrier aeroge of montmorillonite.
Embodiment 7
It takes 0.6g lauryl sodium sulfate (SDS), 0.01g deca-BDE to be added in 100g water, after sonic oscillation 2h, adds Enter the carbon nanotube of 0.8g, ultrasonic disperse 1h obtains dispersion liquid；1.5h is kept after above-mentioned dispersion liquid is vacuumized, is then restored To normal pressure, repeats vacuum step three times, obtain carbon nanotube carrier wet gel；0.09g montmorillonite is dry at 155 DEG C 7h, then the montmorillonite dispersions that mass fraction is 0.06wt% are configured to solvent；By montmorillonite dispersions at 35 DEG C with The speed mechanical of 400r/min stirs 4h, then with the ultrasonic treatment 9h of 288W power, obtains montmorillonite wet gel；0.7g carbon is received Mitron support wet gel, 0.8g montmorillonite wet gel, the ammonium polyphosphate solution that 0.3g mass fraction is 0.05wt% mix, 30 11h is stirred at DEG C, is then sonicated 7h, 6h is finally centrifuged under 2500rpm revolving speed, obtains solution, then place the product in CO2 In supercritical high-pressure extraction device, with CO2Supercritical drying 2h is carried out at 300 DEG C of temperature and air pressure 20MPa for medium, can be obtained To the multiple dimensioned carrier aeroge of carbon nanotube/montmorillonite.
Embodiment 8
It takes 12g lauryl sodium sulfate (SDS), 18g deca-BDE to be added in 100g water, after sonic oscillation 31h, is added The carbon nanotube of 12g, ultrasonic disperse 8h, obtains dispersion liquid；1h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to often Pressure repeats vacuum step three times, obtains carbon nanotube carrier wet gel；20h is dried into 12g montmorillonite at 133 DEG C, then is used Solvent is configured to the montmorillonite dispersions that mass fraction is 24wt%；By montmorillonite dispersions with the speed of 365r/min at 20 DEG C Mechanical stirring 9h is spent, then with the ultrasonic treatment 13h of 92W power, obtains montmorillonite wet gel；32g carbon nanotube carrier is wet solidifying Glue, 30g montmorillonite wet gel, the ammonium polyphosphate solution that 16g mass fraction is 18wt% mix, and 20h is stirred at 12.5 DEG C, then It is ultrasonically treated 15h, 1h is finally centrifuged under 1000rpm revolving speed, obtains solution, then place the product in CO2Supercritical, high pressure extraction It takes in device, with CO2Supercritical drying 1h is carried out at 10 DEG C of temperature and air pressure 1MPa for medium, and carbon nanotube/illiteracy can be obtained The de- multiple dimensioned carrier aeroge of soil.
Flame retardant property test:
The material and EVA (mass ratio 1:4) for taking the method for the invention to prepare, are warming up to 140 DEG C for mixer, 45 EVA is added under conditions of rev/min, the material of invention the method preparation is added after constant torque, keeps 10min to mixing Uniformly.Composite material after mixing is put into vulcanizing press, sample processed is molded with 140 DEG C of 10MPa, is placed on dry and ventilated Place is for 24 hours.According to GB/T2406.2-2009, GB8624-2006 and document (Li Bin, Wang Jianqi, polymer material flammability and resistance Evaluation --- cone calorimetry (CONE) method of combustion property, polymer material science and engineering, 1998,14:15) the method measurement Composite material limit oxygen index, maximum heatrelease rate and ignitor firing time, the results are shown in Table 1.
The flame retardant property of 1 material of table
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal Fall into protection scope of the present invention.

Claims (10)

1. with mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material, it is characterised in that: carbon nanotube- Montmorillonite Composite aerogel material average specific surface area is 601-604m2g-1, in carbon nanotube-montmorillonite Composite aerogel material Exist simultaneously nanoscale and micro-meter scale hole, nanoscale hole average out to 10-11nm, micro-meter scale hole average out to It 19-21 μm, carries out as steps described below:
Step 1, take 0.6-12 parts by weight lauryl sodium sulfate (SDS), 0.01-18 parts by weight deca-BDE that 100 weights are added It measures in part water, after sonic oscillation is uniform, the carbon nanotube of 0.8-12 parts by weight is added thereto, after ultrasonic disperse is uniform, take out true Vacuum is kept after sky, is then restored to normal pressure, is repeated vacuum step three times, is obtained the wet gel of step 1；
Step 2, by after 0.09-12 parts by weight montmorillonite drying, the montmorillonite dispersions of 0.06-24wt% are configured to solvent, Montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the wet gel of step 2；
Step 3, by the wet gel of 0.7-32 parts by weight step 1, the wet gel of 0.8-30 parts by weight step 2,0.3-16 parts by weight The ammonium polyphosphate solution that mass fraction is 0.05-18wt% mixes, and stirs evenly after being then sonicated centrifugation, obtains product, will Product is placed in CO2In supercritical high-pressure extraction device, with CO2Surpassed at 10-300 DEG C of temperature and air pressure 1-20MPa for medium Critical drying at least 1h can obtain having mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material.
2. according to claim 1 have mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material, It is characterized in that: in step 1,1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight deca-BDE being added Enter in water, after sonic oscillation 2-48h, the carbon nanotube of 1-10 parts by weight is added thereto, after ultrasonic disperse 1-24h, vacuumizes After keep 0.5-2h.
3. according to claim 1 have mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material, It is characterized in that: in step 2,5-20h is dried into the montmorillonite of 0.1-10 parts by weight at 60-180 DEG C, is configured to 0.1- with solvent Montmorillonite dispersions are stirred 4- at 5-35 DEG C with the speed mechanical of 150-400r/min by the montmorillonite dispersions of 20wt% 10h, then the ultrasonic treatment 6-15h with 50-300W power.
4. according to claim 1 have mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material, It is characterized in that: in step 3,1-30 parts by weight of carbon nanotubes being carried into medicine wet gel, 1-30 parts by weight montmorillonite wet gel, 0.5- The ammonium polyphosphate solution that 15 parts by weight mass fractions are 0.05-15wt% mixes, and 10-25h is stirred at 5-35 DEG C, is ultrasonically treated 6-15h is finally centrifuged 1-8h under 1000-3500rpm revolving speed.
5. according to claim 1 have mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material, Be characterized in that: in step 3, the supercritical drying time is 2-4h, preferably 3h.
6. with mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material preparation method, it is characterised in that: It carries out as steps described below:
Step 1, take 0.6-12 parts by weight lauryl sodium sulfate (SDS), 0.01-18 parts by weight deca-BDE that 100 weights are added It measures in part water, after sonic oscillation is uniform, the carbon nanotube of 0.8-12 parts by weight is added thereto, after ultrasonic disperse is uniform, take out true Vacuum is kept after sky, is then restored to normal pressure, is repeated vacuum step three times, is obtained the wet gel of step 1；
Step 2, by after 0.09-12 parts by weight montmorillonite drying, the montmorillonite dispersions of 0.06-24wt% are configured to solvent, Montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the wet gel of step 2；
Step 3, by the wet gel of 0.7-32 parts by weight step 1, the wet gel of 0.8-30 parts by weight step 2,0.3-16 parts by weight The ammonium polyphosphate solution that mass fraction is 0.05-18wt% mixes, and stirs evenly after being then sonicated centrifugation, obtains product, will Product is placed in CO2In supercritical high-pressure extraction device, with CO2Surpassed at 10-300 DEG C of temperature and air pressure 1-20MPa for medium Critical drying at least 1h can obtain having mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material.
7. according to claim 1 with mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material Preparation method, it is characterised in that: in step 1, by 1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight ten Dibromodiphenyl ether is added to the water, and after sonic oscillation 2-48h, the carbon nanotube of 1-10 parts by weight, ultrasonic disperse 1-24h are added thereto Afterwards, 0.5-2h is kept after vacuumizing.
8. according to claim 1 with mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material Preparation method, it is characterised in that: in step 2, dry 5-20h, use are molten at 60-180 DEG C by the montmorillonite of 0.1-10 parts by weight Agent is configured to the montmorillonite dispersions of 0.1-20wt%, by montmorillonite dispersions with the speed of 150-400r/min at 5-35 DEG C Mechanical stirring 4-10h, then the ultrasonic treatment 6-15h with 50-300W power.
9. according to claim 1 with mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material Preparation method, it is characterised in that: in step 3,1-30 parts by weight of carbon nanotubes is carried into medicine wet gel, 1-30 parts by weight montmorillonite Wet gel, the ammonium polyphosphate solution that 0.5-15 parts by weight mass fraction is 0.05-15wt% mix, and stir 10- at 5-35 DEG C 25h is ultrasonically treated 6-15h, is finally centrifuged 1-8h under 1000-3500rpm revolving speed.
10. according to claim 1 with mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material Preparation method, it is characterised in that: in step 3, the supercritical drying time is 2-4h, preferably 3h.
CN201810006069.3A 2018-01-03 2018-01-03 With mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof Pending CN109988339A (en)

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WO2016186354A1 (en) * 2015-05-20 2016-11-24 임기태 2k mica flake paint composition forming breathable layer structure, preparation method thereof, and functional film and functional board using the same and forming method thereof
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CN101608060A (en) * 2009-07-09 2009-12-23 中国科学技术大学 Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and method for making thereof
CN102532597A (en) * 2010-12-24 2012-07-04 中国石油化工股份有限公司 Halloysite/montmorillonoid composite powder and preparation method and application thereof
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Application publication date: 20190709