CN109984992A - Three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof - Google Patents

Three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof Download PDF

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CN109984992A
CN109984992A CN201810005730.9A CN201810005730A CN109984992A CN 109984992 A CN109984992 A CN 109984992A CN 201810005730 A CN201810005730 A CN 201810005730A CN 109984992 A CN109984992 A CN 109984992A
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montmorillonite
carbon nanotube
weight
parts
wet gel
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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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Tianjin Chengjian University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/34—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide
    • A61K31/341—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide not condensed with another ring, e.g. ranitidine, furosemide, bufetolol, muscarine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
    • A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
    • A61K31/4422—1,4-Dihydropyridines, e.g. nifedipine, nicardipine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/0087—Galenical forms not covered by A61K9/02 - A61K9/7023
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels

Abstract

The present invention provides three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof, after preparing the wet gel and montmorillonite wet gel that carbon nanotube carries frusemide respectively, after the two is mixed with nitre benzene arsenic heavy stone used as an anchor solution, three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material is made.With gradually increasing for soaking time, the drug nitre benzene arsenic heavy stone used as an anchor being carried in mesoporous takes the lead in discharging, and with further increasing for soaking time, the subsequent release of frusemide drug being carried in micropore realizes primary medication, the effect of multiple dosing.

Description

Three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof
Technical field
The present invention relates to technical field of nano material, more specifically to a kind of three-dimensional netted carbon nanotube-montmorillonite Aerogel composite 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 three-dimensional netted carbon nanotube-montmorillonite Composite gas Gel rubber material and preparation method thereof uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilizes The meso-hole structure of aeroge and the microcellular structure of fiber, load different pharmaceutical respectively, realize the ladder-like classification release of drug.
The purpose of the present invention is achieved by following technical proposals.
Three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof carries out as steps described below:
Step 1, take 0.5-15 parts by weight lauryl sodium sulfate (SDS), 0.01-20 parts by weight frusemide that 100 weights are added It measures in part water, after sonic oscillation is uniform, the carbon nanotube of 0.5-15 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 0.05-15 parts by weight montmorillonite drying, dispersed with the montmorillonite that solvent is configured to 0.05-25wt% 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 0.5-35 parts by weight step 1, the wet gel of 0.5-30 parts by weight step 2,0.1-20 weight It measures the nitre benzene arsenic heavy stone used as an anchor solution that part mass fraction is 0.05-20wt% 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, three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material can be obtained.
In step 1, water is added in 1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight frusemide 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 1h.
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 nitre benzene arsenic heavy stone used as an anchor 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 frusemide being added in step 1 is dispersed in carbon nanotube hollow structure, and carbon nanotube hollow structure is three-dimensional Mesh carbon nanotube-montmorillonite Composite aerogel material provides microcellular structure, frusemide 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 three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material, while nitre benzene arsenic heavy stone used as an anchor being loaded 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 602.14m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, surveys through multiple groups The average specific surface area for measuring material is 600-608m2g-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=-0.997/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.390 [- 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 10.09nm, another kind are 20.87 μm, are measured through multiple groups, and nanoscale hole is average up to 10-12nm, and micro-meter scale hole is flat Up to 20-22 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.
Reference literature (Li Degui, the preparation and characterization of nano-cellulose base Thermosensitive Material Used for Controlled Releasing of Medicine, South China Science & Engineering University, 2016) method described in carries out sustained release performance test characterization to material prepared by the present invention.Two sustained release steps are delayed respectively It releases product and carries out infrared spectroscopy detection, as a result as shown in figure 3, by being compareed with standard diagram, it was demonstrated that take the lead in release is nitre benzene Pyridine, what is then discharged is frusemide, realizes the multiple dimensioned load and repeatedly release of different pharmaceutical.
The composite material carrying medicament prepared using the method for the invention is placed in simulation human consumption's liquid, measurement Its drug release effect, figure 4, it is seen that gradually increasing with soaking time, the drug furan plug being carried in mesoporous Rice takes the lead in discharging, and with further increasing for soaking time, the subsequent release of nitre benzene arsenic heavy stone used as an anchor drug being carried in micropore is realized Primary medication, the effect of multiple dosing.
Detailed description of the invention
Fig. 1 is three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material N2Adsorption-desorption curve；
Fig. 2 is three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material electromicroscopic photograph；
Fig. 3 is three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material release product test curve；
Fig. 4 is three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material carrying medicament release profiles.
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 frusemide be added 100g water in, sonic oscillation for 24 hours after, be added 5g's Carbon nanotube, ultrasonic disperse 5h, 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 and carries medicine wet gel；10h is dried into 0.5g montmorillonite at 78 DEG C, then is matched with solvent It is set to the montmorillonite dispersions that mass fraction is 6wt%；By montmorillonite dispersions with the speed mechanical of 190r/min at 26 DEG C 5h is stirred, then with the ultrasonic treatment 11h of 150W power, obtains montmorillonite wet gel；12g carbon nanotube is carried into medicine wet gel, 21g Montmorillonite wet gel, the nitre benzene arsenic heavy stone used as an anchor solution that 0.5g mass fraction is 5.9wt% mix, and are stirred at 19h, then ultrasound at 8 DEG C 6h is managed, 8h is finally centrifuged under 1200rpm revolving speed, obtains solution, then place the product in CO2Supercritical high-pressure extraction device In, with CO2Supercritical drying 3h is carried out at 150 DEG C of temperature and air pressure 10MPa for medium, and carbon nanotube/montmorillonite can be obtained Multiple dimensioned load medicine aeroge.
Embodiment 2
It takes 5g lauryl sodium sulfate (SDS), 5g frusemide to be added in 100g water, after sonic oscillation 2h, the carbon of 3g is added Nanotube, ultrasonic disperse 1h, obtains dispersion liquid；1h is kept after above-mentioned dispersion liquid is vacuumized, is then restored to normal pressure, repeats to take out Vacuum step three times, obtains carbon nanotube and carries medicine wet gel；7h is dried into 5g montmorillonite at 155 DEG C, then is configured to solvent Mass fraction is the montmorillonite dispersions of 2wt%；Montmorillonite dispersions are stirred at 35 DEG C with the speed mechanical of 400r/min 4h, then with the ultrasonic treatment 9h of 288W power, obtain montmorillonite wet gel；13g carbon nanotube is carried into medicine wet gel, 10g is covered and taken off Native wet gel, the nitre benzene arsenic heavy stone used as an anchor solution that 12g mass fraction is 3wt% mix, and stir 11h at 30 DEG C, are then sonicated 7h, most 6h is centrifuged under 2500rpm revolving speed afterwards, obtains solution, then place the product in CO2In supercritical high-pressure extraction device, with CO2For Medium carries out supercritical drying 3h at 300 DEG C of temperature and air pressure 9MPa, and the multiple dimensioned load medicine gas of carbon nanotube/montmorillonite can be obtained Gel.
Embodiment 3
It takes 3g lauryl sodium sulfate (SDS), 15g frusemide to be added in 100g water, after sonic oscillation 16h, is added 6g's Carbon nanotube, ultrasonic disperse 19h, obtains dispersion liquid；1h 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 and carries medicine wet gel；5h is dried into 3g montmorillonite at 180 DEG C, then is matched with solvent It is set to the montmorillonite dispersions that mass fraction is 13wt%；By montmorillonite dispersions with the speed mechanical of 150r/min at 12 DEG C 6h is stirred, then with the ultrasonic treatment 8h of 300W power, obtains montmorillonite wet gel；25g carbon nanotube is carried into medicine wet gel, 30g Montmorillonite wet gel, the nitre benzene arsenic heavy stone used as an anchor solution that 15g mass fraction is 0.05wt% mix, and are stirred at 25h, then ultrasound at 21 DEG C 8h is managed, 5h is finally centrifuged under 3500rpm revolving speed, obtains solution, then place the product in CO2Supercritical high-pressure extraction device In, with CO2Supercritical drying 3h is carried out at 220 DEG C of temperature and air pressure 20MPa for medium, and carbon nanotube/montmorillonite can be obtained Multiple dimensioned load medicine aeroge.
Embodiment 4
It takes 10g lauryl sodium sulfate (SDS), 0.05g frusemide to be added in 100g water, after sonic oscillation 5h, 1g is added Carbon nanotube, ultrasonic disperse for 24 hours, obtains dispersion liquid；1h 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 and carry medicine wet gel；19h is dried into 8g montmorillonite at 95 DEG C, then uses solvent It is configured to the montmorillonite dispersions that mass fraction is 0.6wt%；By montmorillonite dispersions at 5 DEG C with the speed machine of 330r/min Tool stirs 8h, then with the ultrasonic treatment 6h of 50W power, obtains montmorillonite wet gel；30g carbon nanotube is carried into medicine wet gel, 29g Montmorillonite wet gel, the nitre benzene arsenic heavy stone used as an anchor solution that 13g mass fraction is 9.3wt% mix, and are stirred at 10h, then ultrasound at 35 DEG C 10h is managed, 4h is finally centrifuged under 1900rpm revolving speed, obtains solution, then place the product in CO2Supercritical high-pressure extraction device In, with CO2Supercritical drying 3h is carried out at 188 DEG C of temperature and air pressure 12MPa for medium, and carbon nanotube/montmorillonite can be obtained Multiple dimensioned load medicine aeroge.
Embodiment 5
It takes 6g lauryl sodium sulfate (SDS), 3.5g frusemide to be added in 100g water, after sonic oscillation 48h, is added 7g's Carbon nanotube, ultrasonic disperse 10h, obtains dispersion liquid；1h 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 and carries medicine wet gel；15h is dried into 7g montmorillonite at 87 DEG C, then is matched with solvent It is set to the montmorillonite dispersions that mass fraction is 8wt%；Montmorillonite dispersions are stirred at 9 DEG C with the speed mechanical of 290r/min It mixes 10h, then with the ultrasonic treatment 15h of 122W power, obtains montmorillonite wet gel；1g carbon nanotube is carried into medicine wet gel, 16g is covered De- soil wet gel, the nitre benzene arsenic heavy stone used as an anchor solution that 6g mass fraction is 0.9wt% mix, and stir 23h at 5 DEG C, are then sonicated 12h is finally centrifuged 2h under 3000rpm revolving speed, obtains solution, then place the product in CO2In supercritical high-pressure extraction device, With CO2Supercritical drying 3h is carried out at 10 DEG C of temperature and air pressure 1MPa for medium, and it is multiple dimensioned that carbon nanotube/montmorillonite can be obtained Carry medicine aeroge.
Embodiment 6
It takes 9g lauryl sodium sulfate (SDS), 9.7g frusemide to be added in 100g water, after sonic oscillation 31h, 10g is added Carbon nanotube, ultrasonic disperse 8h obtains dispersion liquid；1h 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 and carries medicine wet gel；20h is dried into 5.6g montmorillonite at 133 DEG C, then uses solvent It is configured to the montmorillonite dispersions that mass fraction is 0.1wt%；By montmorillonite dispersions with the speed of 365r/min at 20 DEG C Mechanical stirring 9h, then with the ultrasonic treatment 13h of 92W power, obtain montmorillonite wet gel；By 9g carbon nanotube carry medicine wet gel, 6g montmorillonite wet gel, the nitre benzene arsenic heavy stone used as an anchor solution that 4.6g mass fraction is 15wt% mix, and 20h are stirred at 12.5 DEG C, then surpass Sonication 15h is finally centrifuged 1h under 1000rpm revolving speed, obtains molten2Liquid, then place the product in CO2Supercritical, high pressure extraction In device, with CO2Supercritical drying 3h is carried out at 24 DEG C of temperature and air pressure 5MPa for medium, and it is de- that carbon nanotube/illiteracy can be obtained The multiple dimensioned load medicine aeroge of soil.
Embodiment 7
It takes 0.5g lauryl sodium sulfate (SDS), 0.01g frusemide to be added in 100g water, after sonic oscillation 48h, is added The carbon nanotube of 0.5g, ultrasonic disperse 10h, 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 and carries medicine wet gel；15h is dried into 0.05g montmorillonite at 87 DEG C, then The montmorillonite dispersions that mass fraction is 0.05wt% are configured to solvent；By montmorillonite dispersions with 290r/min at 9 DEG C Speed mechanical stir 10h, then with the ultrasonic treatment 15h of 122W power, obtain montmorillonite wet gel；0.5g carbon nanotube is carried Medicine wet gel, 0.5g montmorillonite wet gel, the nitre benzene arsenic heavy stone used as an anchor solution that 0.1g mass fraction is 0.05wt% 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 4h is carried out at 12 DEG C of temperature and air pressure 1MPa for medium, and carbon can be obtained and receive The multiple dimensioned load medicine aeroge of mitron/montmorillonite.
Embodiment 8
Take 15g lauryl sodium sulfate (SDS), 20g frusemide be added 100g water in, sonic oscillation for 24 hours after, be added 15g Carbon nanotube, ultrasonic disperse 5h obtains dispersion liquid；1h 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 and carries medicine wet gel；10h is dried into 15g montmorillonite at 78 DEG C, then is matched with solvent It is set to the montmorillonite dispersions that mass fraction is 25wt%；By montmorillonite dispersions with the speed mechanical of 190r/min at 26 DEG C 5h is stirred, then with the ultrasonic treatment 11h of 150W power, obtains montmorillonite wet gel；35g carbon nanotube is carried into medicine wet gel, 30g Montmorillonite wet gel, the nitre benzene arsenic heavy stone used as an anchor solution that 20g mass fraction is 20wt% mix, and stir 19h at 8 DEG C, are then sonicated 6h is finally centrifuged 8h under 1200rpm revolving speed, obtains solution, then place the product in CO2In supercritical high-pressure extraction device, With CO2Supercritical drying 2h is carried out at 300 DEG C of temperature and air pressure 20MPa for medium, and the more rulers of carbon nanotube/montmorillonite can be obtained Degree carries medicine aeroge.
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. three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material, it is characterised in that: carbon nanotube-montmorillonite Composite gas Gel rubber material average specific surface area is 600-608m2g-1, nanometer is existed simultaneously in carbon nanotube-montmorillonite Composite aerogel material Scale and micro-meter scale hole, nanoscale hole average out to 10-12nm, 20-22 μm of average out to of micro-meter scale hole, under State step progress:
Step 1, take 0.5-15 parts by weight lauryl sodium sulfate (SDS), 0.01-20 parts by weight frusemide that 100 parts by weight are added In water, after sonic oscillation is uniform, the carbon nanotube of 0.5-15 parts by weight is added thereto, after ultrasonic disperse is uniform, after vacuumizing Vacuum is kept, normal pressure is then restored to, vacuum step is repeated three times, obtains the wet gel of step 1；
Step 2, by after 0.05-15 parts by weight montmorillonite drying, the montmorillonite dispersions of 0.05-25wt% 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 0.5-35 parts by weight step 1, the wet gel of 0.5-30 parts by weight step 2,0.1-20 parts by weight The nitre benzene arsenic heavy stone used as an anchor solution that mass fraction is 0.05-20wt% 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 Three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material can be obtained in critical drying at least 1h.
2. three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: In step 1,1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight frusemide 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 1h after vacuumizing.
3. three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: In step 2,5-20h is dried into the montmorillonite of 0.1-10 parts by weight at 60-180 DEG C, the illiteracy of 0.1-20wt% is configured to solvent Montmorillonite dispersions are stirred 4-10h at 5-35 DEG C with the speed mechanical of 150-400r/min, then use 50- by de- soil dispersion liquid The ultrasonic treatment 6-15h of 300W power.
4. three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material according to claim 1, 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, 0.5-15 parts by weight matter It measures the nitre benzene arsenic heavy stone used as an anchor solution that score is 0.05-15wt% to mix, 10-25h is stirred at 5-35 DEG C, is ultrasonically treated 6-15h, finally 1-8h is centrifuged under 1000-3500rpm revolving speed.
5. three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: In step 3, the supercritical drying time is 2-4h, preferably 3h.
6. three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material preparation method, it is characterised in that: as steps described below It carries out:
Step 1, take 0.5-15 parts by weight lauryl sodium sulfate (SDS), 0.01-20 parts by weight frusemide that 100 parts by weight are added In water, after sonic oscillation is uniform, the carbon nanotube of 0.5-15 parts by weight is added thereto, after ultrasonic disperse is uniform, after vacuumizing Vacuum is kept, normal pressure is then restored to, vacuum step is repeated three times, obtains the wet gel of step 1；
Step 2, by after 0.05-15 parts by weight montmorillonite drying, the montmorillonite dispersions of 0.05-25wt% 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 0.5-35 parts by weight step 1, the wet gel of 0.5-30 parts by weight step 2,0.1-20 parts by weight The nitre benzene arsenic heavy stone used as an anchor solution that mass fraction is 0.05-20wt% 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 Three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material can be obtained in critical drying at least 1h；
The frusemide being added in step 1 is dispersed in carbon nanotube hollow structure, and carbon nanotube hollow structure is three-dimensional netted Carbon nanotube-montmorillonite Composite aerogel material provides microcellular structure, and frusemide is supported in carbon nanotube, carbon nanotube it Between form tridimensional network, the montmorillonite being added in step 2 is successfully configured to network pore structure, above-mentioned tridimensional network It is successfully configured to network pore structure with carbon nanotube and together forms three-dimensional network pore structure, above-mentioned three-dimensional network hole knot Structure provides meso-hole structure for three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material, while nitre benzene arsenic heavy stone used as an anchor is supported on Jie In pore structure.
7. the preparation method of three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material according to claim 6, special Sign is: in step 1,1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight frusemide is added to the water, After sonic oscillation 2-48h, the carbon nanotube of 1-10 parts by weight is added thereto, after ultrasonic disperse 1-24h, is kept after vacuumizing 1h。
8. the preparation method of three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material according to claim 6, special Sign is: in step 2,5-20h is dried in 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 three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material according to claim 6, special Sign is: in step 3,1-30 parts by weight of carbon nanotubes being carried medicine wet gel, 1-30 parts by weight montmorillonite wet gel, 0.5-15 The nitre benzene arsenic heavy stone used as an anchor solution that parts by weight mass fraction is 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.
10. the preparation method of three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material according to claim 6, Be characterized in that: in step 3, the supercritical drying time is 2-4h, preferably 3h.
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* Cited by examiner, † Cited by third party
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