CN109987958A - Multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof - Google Patents
Multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
Abstract
The present invention provides multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof, after preparing the wet gel and montmorillonite wet gel that carbon nanotube carries tetrabromobisphenol A respectively, by the two and boric acid three (2,5-dibromos) propyl ester solution mixing after, multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material is made.It uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilize the meso-hole structure of aeroge and the microcellular structure of fiber, load tetrabromobisphenol A and boric acid three (2 respectively, 5-dibromos) propyl ester, different characteristics fire retardant is combined, realizes cooperative flame retardant effect.
Description
Technical field
The present invention relates to technical field of nano material, multiple more specifically to a kind of multiple dimensioned carbon nanotube-montmorillonite
Close 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 multiple dimensioned carbon nanotube-montmorillonite Composite airsetting
Glue material and preparation method thereof uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilizes gas
The meso-hole structure of gel and the microcellular structure of fiber, load different flame retardant respectively, and different characteristics fire retardant is combined, and realize association
Same flame retardant effect.
The purpose of the present invention is achieved by following technical proposals.
Multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof carries out as steps described below:
Step 1,0.6-12 parts by weight lauryl sodium sulfate (SDS), 0.01-18 parts by weight tetrabromobisphenol A is taken to be added 100
In 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, takes out
Vacuum is kept after vacuum, 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
Measure part mass fraction be 0.05-18wt% (2,5-dibromo) the propyl ester solution of boric acid three mix, stir evenly be then sonicated from
After the heart, product is obtained, place the product in CO2In supercritical high-pressure extraction device, with CO2It is gentle at 10-300 DEG C of temperature for medium
It presses and carries out supercritical drying at least 1h under 1-20MPa, multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material can be obtained.
In step 1,1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight tetrabromobisphenol A 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-
(2,5-dibromo) the propyl ester solution of boric acid three that 15 parts by weight mass fractions are 0.05-15wt% mixes, and stirs at 5-35 DEG C
10-25h 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 tetrabromobisphenol A being added in step 1 is dispersed in carbon nanotube hollow structure, and carbon nanotube hollow structure is more
Scale carbon nanotube-montmorillonite Composite aerogel material provides microcellular structure, tetrabromobisphenol A is supported in carbon nanotube, carbon
Tridimensional network is formed between nanotube, the montmorillonite being added in step 2 is successfully configured to network pore structure, above-mentioned three-dimensional
Reticular structure and carbon nanotube are successfully configured to network pore structure and together form three-dimensional network pore structure, above-mentioned three dimensional network
Network pore structure provides meso-hole structure for multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material, at the same by boric acid three (2,
5-dibromos) propyl ester is 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 603.01m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, surveys through multiple groups
The average specific surface area for measuring material is 600-604m2g-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=-0.929/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.355 [- 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
10.44nm, another kind are 20.49 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 multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material N2Adsorption-desorption curve；
Fig. 2 is multiple dimensioned 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 tetrabromobisphenol A be added 100g water in, sonic oscillation for 24 hours after, be added 5g
Carbon nanotube, ultrasonic disperse 5h obtains dispersion liquid；0.5h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to normal pressure,
It repeats vacuum step three times, obtains carbon nanotube carrier wet gel；By 0.5g montmorillonite at 78 DEG C dry 10h, then with molten
Agent 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, then with the ultrasonic treatment 11h of 150W power, obtain montmorillonite wet gel；12g carbon nanotube carrier is wet solidifying
Glue, 21g montmorillonite wet gel, (2,5-dibromo) the propyl ester solution of boric acid three that 0.5g mass fraction is 5.9wt% mix, at 8 DEG C
Lower stirring 19h, is then sonicated 6h, and 8h is finally centrifuged under 1200rpm revolving speed, obtains solution, then place the product in CO2It is super
In critical high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 150 DEG C of temperature and air pressure 10MPa for medium, can be obtained
The multiple dimensioned carrier aeroge of carbon nanotube/montmorillonite.
Embodiment 2
It takes 5g lauryl sodium sulfate (SDS), 5g tetrabromobisphenol A to be added in 100g water, after sonic oscillation 2h, is added 3g's
Carbon nanotube, ultrasonic disperse 1h, obtains dispersion liquid；1h is kept after above-mentioned dispersion liquid is vacuumized, is then restored to normal pressure, is repeated
Vacuum step three times, obtains carbon nanotube carrier wet gel；7h is dried into 5g montmorillonite at 155 DEG C, then is configured with solvent
The montmorillonite dispersions for being 2wt% at mass fraction；Montmorillonite dispersions are stirred at 35 DEG C with the speed mechanical of 400r/min
It mixes 4h, then with the ultrasonic treatment 9h of 288W power, obtains montmorillonite wet gel；13g carbon nanotube carrier wet gel, 10g are covered
De- soil wet gel, (2,5-dibromo) the propyl ester solution of boric acid three that 12g mass fraction is 3wt% mix, and stir 11h at 30 DEG C,
It is then sonicated 7h, 6h is finally centrifuged under 2500rpm revolving speed, obtains solution, then place the product in CO2Supercritical, high pressure extraction
It takes in device, with CO2Supercritical drying 3h is carried out at 300 DEG C of temperature and air pressure 9MPa for medium, and carbon nanotube/illiteracy can be obtained
The de- multiple dimensioned carrier aeroge of soil.
Embodiment 3
It takes 3g lauryl sodium sulfate (SDS), 15g tetrabromobisphenol A to be added in 100g water, after sonic oscillation 16h, 6g is added
Carbon nanotube, 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, (2,5-dibromo) the propyl ester solution of boric acid three that 15g mass fraction is 0.05wt% mix, at 21 DEG C
25h is stirred, 8h is then sonicated, 5h is finally centrifuged under 3500rpm revolving speed, obtains solution, then place the product in CO2It is super to face
In boundary's high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 220 DEG C of temperature and air pressure 20MPa for medium, and carbon can be obtained
The multiple dimensioned carrier aeroge of nanotube/montmorillonite.
Embodiment 4
It takes 10g lauryl sodium sulfate (SDS), 0.05g tetrabromobisphenol A to be added in 100g water, after sonic oscillation 5h, is added
The carbon nanotube of 1g, ultrasonic disperse for 24 hours, obtain 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 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, (2,5-dibromo) the propyl ester solution of boric acid three that 13g mass fraction is 9.3wt% mix, at 35 DEG C
10h is stirred, 10h is then sonicated, 4h is finally centrifuged under 1900rpm revolving speed, obtains solution, then place the product in CO2It is super
In critical high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 188 DEG C of temperature and air pressure 12MPa for medium, can be obtained
The multiple dimensioned carrier aeroge of carbon nanotube/montmorillonite.
Embodiment 5
It takes 6g lauryl sodium sulfate (SDS), 3.5g tetrabromobisphenol A 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, (2,5-dibromo) the propyl ester solution of boric acid three that 6g mass fraction is 0.9wt% mix, and stir at 5 DEG C
23h is mixed, 12h is then sonicated, 2h is finally centrifuged under 3000rpm revolving speed, obtains solution, then place the product in CO2It is super to face
In boundary's high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 10 DEG C of temperature and air pressure 1MPa for medium, and carbon can be obtained and receive
The multiple dimensioned carrier aeroge of mitron/montmorillonite.
Embodiment 6
It takes 9g lauryl sodium sulfate (SDS), 9.7g tetrabromobisphenol A to be added in 100g water, after sonic oscillation 31h, is added
The carbon nanotube of 10g, ultrasonic disperse 8h, 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；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, (2,5-dibromo) the propyl ester solution of boric acid three that 4.6g mass fraction is 15wt% mix,
20h is stirred at 12.5 DEG C, is then sonicated 15h, 1h is finally centrifuged under 1000rpm revolving speed, solution is obtained, then sets product
In CO2In supercritical high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 24 DEG C of temperature and air pressure 5MPa for medium, it can
Obtain the multiple dimensioned carrier aeroge of carbon nanotube/montmorillonite.
Embodiment 7
Take 12g lauryl sodium sulfate (SDS), 18g tetrabromobisphenol A be added 100g water in, sonic oscillation for 24 hours after, be added
The carbon nanotube of 12g, ultrasonic disperse 5h, 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；10h is dried into 12g montmorillonite at 78 DEG C, then is used
Solvent is configured to the montmorillonite dispersions that mass fraction is 24wt%；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；32g carbon nanotube carrier is wet solidifying
Glue, 30g montmorillonite wet gel, (2,5-dibromo) the propyl ester solution of boric acid three that 16g mass fraction is 18wt% mix, at 8 DEG C
19h is stirred, 6h is then sonicated, 8h is finally centrifuged under 1200rpm revolving speed, obtains solution, then place the product in CO2It is super to face
In boundary's high-pressure extraction device, with CO2Supercritical drying 4h is carried out at 300 DEG C of temperature and air pressure 12MPa for medium, and carbon can be obtained
The multiple dimensioned carrier aeroge of nanotube/montmorillonite.
Embodiment 8
It takes 0.6g lauryl sodium sulfate (SDS), 0.01g tetrabromobisphenol A to be added in 100g water, after sonic oscillation 5h, adds
Enter the carbon nanotube of 0.8g, ultrasonic disperse for 24 hours, obtains dispersion liquid；0.5h 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 95 DEG C
19h, then the montmorillonite dispersions that mass fraction is 0.06wt% are configured to solvent；By montmorillonite dispersions at 5 DEG C with
The speed mechanical of 330r/min stirs 8h, then with the ultrasonic treatment 6h of 50W power, obtains montmorillonite wet gel；0.7g carbon is received
Mitron support wet gel, 0.8g montmorillonite wet gel, boric acid three (2,5-dibromo) propyl ester that 0.3g mass fraction is 0.05wt%
Solution mixing, stirs 10h at 35 DEG C, is then sonicated 10h, and 4h is finally centrifuged under 1900rpm revolving speed, obtains solution, so
Place the product in CO afterwards2In supercritical high-pressure extraction device, with CO2Super face is carried out at 10 DEG C of temperature and air pressure 1MPa for medium
2h is dried on boundary, and the multiple dimensioned carrier aeroge of carbon nanotube/montmorillonite can be obtained.
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. multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material, it is characterised in that: carbon nanotube-montmorillonite Composite airsetting
Glue material average specific surface area is 600-604m2g-1, a nanometer ruler is existed simultaneously in carbon nanotube-montmorillonite Composite aerogel material
Degree and micro-meter scale hole, nanoscale hole average out to 10-11nm, 19-21 μm of average out to of micro-meter scale hole, according to following
Step carries out:
Step 1, take 0.6-12 parts by weight lauryl sodium sulfate (SDS), 0.01-18 parts by weight tetrabromobisphenol A that 100 weight are added
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, vacuumizes
After keep vacuum, be then restored to normal pressure, repeat vacuum step three times, obtain 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
(2,5-dibromo) the propyl ester solution of boric acid three that mass fraction is 0.05-18wt% mixes, and stirs evenly and is then sonicated centrifugation
Afterwards, product is obtained, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 10-300 DEG C of temperature and air pressure
Supercritical drying at least 1h is carried out under 1-20MPa, and multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material can be obtained.
2. multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step
In rapid 1,1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight tetrabromobisphenol A are added to the water, sonic oscillation
After 2-48h, the carbon nanotube of 1-10 parts by weight is added thereto, after ultrasonic disperse 1-24h, keeps 0.5-2h after vacuumizing.
3. multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step
In rapid 2, by the montmorillonite of 0.1-10 parts by weight, dry 5-20h, the illiteracy for being configured to 0.1-20wt% with solvent are de- at 60-180 DEG C
Montmorillonite dispersions are stirred 4-10h at 5-35 DEG C with the speed mechanical of 150-400r/min, then use 50- by native dispersion liquid
The ultrasonic treatment 6-15h of 300W power.
4. multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step
In rapid 3,1-30 parts by weight of carbon nanotubes is carried into medicine wet gel, 1-30 parts by weight montmorillonite wet gel, 0.5-15 parts by weight quality
(2,5-dibromo) the propyl ester solution of boric acid three that score is 0.05-15wt% mixes, and stirs 10-25h at 5-35 DEG C, at ultrasound
6-15h is managed, is finally centrifuged 1-8h under 1000-3500rpm revolving speed.
5. multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step
In rapid 3, the supercritical drying time is 2-4h, preferably 3h.
6. multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material preparation method, it is characterised in that: as steps described below into
Row:
Step 1, take 0.6-12 parts by weight lauryl sodium sulfate (SDS), 0.01-18 parts by weight tetrabromobisphenol A that 100 weight are added
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, vacuumizes
After keep vacuum, be then restored to normal pressure, repeat vacuum step three times, obtain 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
(2,5-dibromo) the propyl ester solution of boric acid three that mass fraction is 0.05-18wt% mixes, and stirs evenly and is then sonicated centrifugation
Afterwards, product is obtained, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 10-300 DEG C of temperature and air pressure
Supercritical drying at least 1h is carried out under 1-20MPa, and multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material can be obtained；
The tetrabromobisphenol A being added in step 1 is dispersed in carbon nanotube hollow structure, and carbon nanotube hollow structure is multiple dimensioned
Carbon nanotube-montmorillonite Composite aerogel material provides microcellular structure, tetrabromobisphenol A is supported in carbon nanotube, carbon nanometer
Tridimensional network is formed between pipe, the montmorillonite being added in step 2 is successfully configured to network pore structure, above-mentioned three-dimensional netted
Structure and carbon nanotube are successfully configured to network pore structure and together form three-dimensional network pore structure, above-mentioned three-dimensional network hole
Gap structure provides meso-hole structure for multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material, while by boric acid three (2,5-two
Bromine) propyl ester is supported in meso-hole structure.
7. the preparation method of multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material according to claim 6, feature
It is: in step 1, water is added in 1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight tetrabromobisphenol A
In, after sonic oscillation 2-48h, the carbon nanotube of 1-10 parts by weight is added thereto, after ultrasonic disperse 1-24h, is protected after vacuumizing
Hold 0.5-2h.
8. the preparation method of multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material according to claim 6, feature
It is: 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.
9. the preparation method of multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material according to claim 6, feature
It is: 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, 0.5-15 weight
It measures (2,5-dibromo) the propyl ester solution of boric acid three that part mass fraction is 0.05-15wt% to mix, stirs 10- at 5-35 DEG C
25h is ultrasonically treated 6-15h, is finally centrifuged 1-8h under 1000-3500rpm revolving speed.
10. the preparation method of multiple dimensioned carbon nanotube-montmorillonite Composite aerogel material according to claim 6, special
Sign is: in step 3, the supercritical drying time is 2-4h, preferably 3h.
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| EP2440322B1 (en) * | 2009-06-11 | 2017-02-01 | Case Western Reserve University | Polymer reinforced porous material and method of making same |
| CN102153102A (en) * | 2010-11-26 | 2011-08-17 | 北京航空航天大学 | Polyimide reinforced clay aerogel material and preparation method thereof |
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