CN109985579A - Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof - Google Patents

Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof Download PDF

Info

Publication number
CN109985579A
CN109985579A CN201810005729.6A CN201810005729A CN109985579A CN 109985579 A CN109985579 A CN 109985579A CN 201810005729 A CN201810005729 A CN 201810005729A CN 109985579 A CN109985579 A CN 109985579A
Authority
CN
China
Prior art keywords
carbon nanotube
montmorillonite
weight
parts
mesoporous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201810005729.6A
Other languages
Chinese (zh)
Inventor
李洪彦
付永强
刘洪丽
魏冬青
李海明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Chengjian University
Original Assignee
Tianjin Chengjian University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Chengjian University filed Critical Tianjin Chengjian University
Priority to CN201810005729.6A priority Critical patent/CN109985579A/en
Publication of CN109985579A publication Critical patent/CN109985579A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/56Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
    • A61K31/57Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane or progesterone
    • A61K31/573Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane or progesterone substituted in position 21, e.g. cortisone, dexamethasone, prednisone or aldosterone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/70Carbohydrates; Sugars; Derivatives thereof
    • A61K31/7028Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages
    • A61K31/7034Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages attached to a carbocyclic compound, e.g. phloridzin
    • A61K31/7036Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages attached to a carbocyclic compound, e.g. phloridzin having at least one amino group directly attached to the carbocyclic ring, e.g. streptomycin, gentamycin, amikacin, validamycin, fortimicins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02Inorganic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/0087Galenical forms not covered by A61K9/02 - A61K9/7023
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091Preparation of aerogels, e.g. xerogels

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Medicinal Preparation (AREA)

Abstract

The present invention provides mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof, after preparing the wet gel and montmorillonite wet gel that carbon nanotube carries dexamethasone respectively, after the two is mixed with gentamycin solution, mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material is made.With gradually increasing for soaking time, the drug gentamicin being carried in mesoporous takes the lead in discharging, and with further increasing for soaking time, the subsequent release of dexamethasone drug being carried in micropore realizes primary medication, the effect of multiple dosing.

Description

Mesoporous-micropore 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 the mesoporous-micropore carbon nanotube-Meng Tuo of one kind Native 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 mesoporous-micropore 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.
Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof carries out as steps described below:
Step 1,0.5-15 parts by weight lauryl sodium sulfate (SDS), 0.01-20 parts by weight dexamethasone is taken to be added 100 In parts by weight water, after sonic oscillation is uniform, the carbon nanotube of 0.5-15 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 0.05-15 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 gentamycin 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, mesoporous-micropore 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 dexamethasone 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 gentamycin 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 dexamethasone being added in step 1 is dispersed in carbon nanotube hollow structure, and carbon nanotube hollow structure is to be situated between Hole-micropore carbon nanotube-montmorillonite Composite aerogel material provides microcellular structure, and dexamethasone is supported in carbon nanotube, Forming tridimensional network between carbon nanotube, the montmorillonite being added in step 2 is successfully configured to network pore structure, and above-mentioned three Dimension 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 pore structure provides meso-hole structure for mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material, while will celebrate big mould Element 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 attached drawing 1.It can from figure To 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 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, it can be with Sample interior is found out there are more micropore, is as caused by absorption potential strong inside micropore.By nitrogen adsorption desorption isotherm number According to the sample specific surface area can reach 602.14m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, through more The average specific surface area of group measurement 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=-0.964/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.362 [- 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 10.38nm, another kind are 20.41 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 that celebrating is big Mycin, what is then discharged is dexamethasone, 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, fills in the drug being carried in mesoporous Meter Song takes the lead in discharging, and with further increasing for soaking time, the subsequent release of gentamicin drug being carried in micropore is realized Primary medication, the effect of multiple dosing.
Detailed description of the invention
Fig. 1 is mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material N2Adsorption-desorption curve;
Fig. 2 is mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material electromicroscopic photograph;
Fig. 3 is mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material release product test curve;
Fig. 4 is mesoporous-micropore 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 dexamethasone be added 100g water in, sonic oscillation for 24 hours after, be added 5g 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 0.5g montmorillonite at 78 DEG C, then uses solvent It is configured to the montmorillonite dispersions that mass fraction is 6wt%;By montmorillonite dispersions with the speed machine of 190r/min at 26 DEG C Tool stirs 5h, then with the ultrasonic treatment 11h of 150W power, obtains montmorillonite wet gel;By 12g carbon nanotube carry medicine wet gel, 21g montmorillonite wet gel, the gentamycin solution that 0.5g mass fraction is 5.9wt% mix, and 19h, then ultrasound are stirred at 8 DEG C 6h is handled, 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 dexamethasone 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 and carries medicine 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 is carried into medicine wet gel, 10g is covered De- soil wet gel, the gentamycin solution that 12g mass fraction is 3wt% mix, and stir 11h at 30 DEG C, are then sonicated 7h, It is finally centrifuged 6h under 2500rpm revolving speed, obtains solution, then place the product in CO2In supercritical high-pressure extraction device, with CO2 Supercritical drying 3h is carried out at 300 DEG C of temperature and air pressure 9MPa for medium, and the multiple dimensioned load medicine of carbon nanotube/montmorillonite can be obtained Aeroge.
Embodiment 3
It takes 3g lauryl sodium sulfate (SDS), 15g dexamethasone to be added in 100g water, after sonic oscillation 16h, 6g is added 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, It repeats vacuum step three times, obtains carbon nanotube and carry medicine wet gel;5h is dried into 3g montmorillonite at 180 DEG C, then uses solvent It is configured to the montmorillonite dispersions that mass fraction is 13wt%;By montmorillonite dispersions with the speed machine of 150r/min at 12 DEG C Tool stirs 6h, then with the ultrasonic treatment 8h of 300W power, obtains montmorillonite wet gel;By 25g carbon nanotube carry medicine wet gel, 30g montmorillonite wet gel, the gentamycin 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 load medicine aeroge of soil.
Embodiment 4
It takes 10g lauryl sodium sulfate (SDS), 0.05g dexamethasone 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;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;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 carry medicine wet gel, 29g montmorillonite wet gel, the gentamycin 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 load medicine aeroge of soil.
Embodiment 5
It takes 6g lauryl sodium sulfate (SDS), 3.5g dexamethasone to be added in 100g water, after sonic oscillation 48h, 7g is added 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, It repeats vacuum step three times, obtains carbon nanotube and carry medicine wet gel;15h is dried into 7g montmorillonite at 87 DEG C, then uses solvent It is configured to the montmorillonite dispersions that mass fraction is 8wt%;By montmorillonite dispersions with the speed mechanical of 290r/min at 9 DEG C 10h is stirred, then with the ultrasonic treatment 15h of 122W power, obtains montmorillonite wet gel;1g carbon nanotube is carried into medicine wet gel, 16g Montmorillonite wet gel, the gentamycin 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 dexamethasone to be added in 100g water, after sonic oscillation 31h, is added The carbon nanotube of 10g, 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 and carries medicine 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;It is wet that 9g carbon nanotube is carried into medicine Gel, 6g montmorillonite wet gel, the gentamycin 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 load medicine aeroge of montmorillonite.
Embodiment 7
It takes 15g lauryl sodium sulfate (SDS), 20g dexamethasone to be added in 100g water, after sonic oscillation 5h, 15g 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 15g montmorillonite at 95 DEG C, then uses solvent It is configured to the montmorillonite dispersions that mass fraction is 25wt%;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;35 carbon nanotubes are carried into medicine wet gel, 30g Montmorillonite wet gel, the gentamycin solution that 20g mass fraction is 20wt% mix, and stir 10h at 35 DEG C, are then sonicated 10h is finally centrifuged 4h under 1900rpm revolving speed, obtains solution, then place the product in CO2In supercritical high-pressure extraction device, With CO2Supercritical drying 2h is carried out at 268 DEG C of temperature and air pressure 15MPa for medium, and the more rulers of carbon nanotube/montmorillonite can be obtained Degree carries medicine aeroge.
Embodiment 8
It takes 0.5g lauryl sodium sulfate (SDS), 0.01g dexamethasone to be added in 100g water, after sonic oscillation 16h, adds Enter the carbon nanotube of 0.5g, ultrasonic disperse 19h obtains dispersion liquid;1h is kept after above-mentioned dispersion liquid is vacuumized, and is then restored to Normal pressure repeats vacuum step three times, obtains carbon nanotube and carries medicine wet gel;5h is dried into 0.05g montmorillonite at 180 DEG C, The montmorillonite dispersions that mass fraction is 0.05wt% are configured to solvent again;By montmorillonite dispersions with 150r/ at 12 DEG C The speed mechanical of min stirs 6h, then with the ultrasonic treatment 8h of 300W power, obtains montmorillonite wet gel;By 0.5g carbon nanotube It carries medicine wet gel, 0.5g montmorillonite wet gel, the gentamycin solution that 0.1g mass fraction is 0.05wt% to 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 2h is carried out at 22 DEG C of temperature and air pressure 2MPa for medium, and carbon can be obtained and receive The multiple dimensioned load medicine aeroge of mitron/montmorillonite.
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. mesoporous-micropore 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 dexamethasone that 100 weight are added 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, 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 0.05-15 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 gentamycin 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 Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material can be obtained in critical drying at least 1h;
The dexamethasone being added in step 1 is dispersed in carbon nanotube hollow structure, and carbon nanotube hollow structure is mesoporous-micro- Hole carbon nanotube-montmorillonite Composite aerogel material provides microcellular structure, dexamethasone 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, while gentamicin being loaded for mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material In meso-hole structure.
2. mesoporous-micropore 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 dexamethasone are added to the water, ultrasound vibration After swinging 2-48h, the carbon nanotube of 1-10 parts by weight is added thereto, after ultrasonic disperse 1-24h, keeps 1h after vacuumizing.
3. mesoporous-micropore 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. mesoporous-micropore 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 gentamycin 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. mesoporous-micropore 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. mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material preparation method, it is characterised in that: according to following steps It is rapid to carry out:
Step 1, take 0.5-15 parts by weight lauryl sodium sulfate (SDS), 0.01-20 parts by weight dexamethasone that 100 weight are added 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, 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 0.05-15 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 gentamycin 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 Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material can be obtained in critical drying at least 1h;
The dexamethasone being added in step 1 is dispersed in carbon nanotube hollow structure, and carbon nanotube hollow structure is mesoporous-micro- Hole carbon nanotube-montmorillonite Composite aerogel material provides microcellular structure, dexamethasone 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, while gentamicin being loaded for mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material In meso-hole structure.
7. mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material preparation method according to claim 1, It is characterized in that: in step 1,1-10 parts by weight lauryl sodium sulfate (SDS), 0.05-15 parts by weight dexamethasone being 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 1h.
8. mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material preparation method according to claim 1, 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.
9. mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material preparation method according to claim 1, 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 gentamycin 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.
10. mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material preparation method according to claim 1, Be characterized in that: in step 3, the supercritical drying time is 2-4h, preferably 3h.
CN201810005729.6A 2018-01-03 2018-01-03 Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof Withdrawn CN109985579A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810005729.6A CN109985579A (en) 2018-01-03 2018-01-03 Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810005729.6A CN109985579A (en) 2018-01-03 2018-01-03 Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN109985579A true CN109985579A (en) 2019-07-09

Family

ID=67128465

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810005729.6A Withdrawn CN109985579A (en) 2018-01-03 2018-01-03 Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109985579A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004054389A1 (en) * 2004-11-11 2006-05-18 Rehau Ag + Co. Partially crystalline polyamide based polymeric material composition, useful for preparing molded parts e.g. tubes and hoses, comprises partially crystallized polyamide, surface-active substances and active component (amorphous compounds)
CN101129401A (en) * 2005-09-27 2008-02-27 南方医科大学 Nano antibiotic montmorillonite and method of preparing the same
CN102218143A (en) * 2011-06-10 2011-10-19 郑州大学 Water dispersion type carbon nano-tube freeze-dried powder and preparation method thereof
CN105315482A (en) * 2015-12-02 2016-02-10 南京林业大学 Anisotropic nano-cellulose/montmorillonite composite aerogel and preparation method thereof
CN105565774A (en) * 2015-05-11 2016-05-11 天津城建大学 High-strength high-thermal-insulation silica aerogel and preparation method thereof
CN107281982A (en) * 2016-04-05 2017-10-24 中国科学院化学研究所 A kind of adjustable graphene of hydrophilic and hydrophobic/clay composite elastic aeroge and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004054389A1 (en) * 2004-11-11 2006-05-18 Rehau Ag + Co. Partially crystalline polyamide based polymeric material composition, useful for preparing molded parts e.g. tubes and hoses, comprises partially crystallized polyamide, surface-active substances and active component (amorphous compounds)
CN101129401A (en) * 2005-09-27 2008-02-27 南方医科大学 Nano antibiotic montmorillonite and method of preparing the same
CN102218143A (en) * 2011-06-10 2011-10-19 郑州大学 Water dispersion type carbon nano-tube freeze-dried powder and preparation method thereof
CN105565774A (en) * 2015-05-11 2016-05-11 天津城建大学 High-strength high-thermal-insulation silica aerogel and preparation method thereof
CN105315482A (en) * 2015-12-02 2016-02-10 南京林业大学 Anisotropic nano-cellulose/montmorillonite composite aerogel and preparation method thereof
CN107281982A (en) * 2016-04-05 2017-10-24 中国科学院化学研究所 A kind of adjustable graphene of hydrophilic and hydrophobic/clay composite elastic aeroge and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
于金刚: "碳纳米管作为药物载体的研究进展", 《药学学报》 *

Similar Documents

Publication Publication Date Title
Khushnood et al. Carbonized nano/microparticles for enhanced mechanical properties and electromagnetic interference shielding of cementitious materials
Geng et al. Well-dispersed cellulose nanocrystals in hydrophobic polymers by in situ polymerization for synthesizing highly reinforced bio-nanocomposites
Liu et al. Organoclay-modified high performance epoxy nanocomposites
Raj et al. Nanomaterials in geopolymer composites: A review
Wang et al. Relationship between dispersion state and reinforcement effect of graphene oxide in microcrystalline cellulose–graphene oxide composite films
Du et al. Methylcellulose stabilized multi-walled carbon nanotubes dispersion for sustainable cement composites
Chen et al. Porous mullite ceramics with a fully closed-cell structure fabricated by direct coagulation casting using fly ash hollow spheres/kaolin suspension
Sun et al. Fabrication of 3D structures via direct ink writing of kaolin/graphene oxide composite suspensions at ambient temperature
Liao et al. Rheological premonitory of nanoclay morphology on the mechanical characteristics of composite aerogels
Dowling et al. The influence of montmorillonite clay reinforcement on the performance of a glass ionomer restorative
Constantinescu et al. Mechanical properties of epoxy nanocomposites reinforced with functionalized silica nanoparticles
Pietrzak et al. Diglyceryl acrylate as alternative additive dedicated to colloidal shaping of oxide materials–synthesis, characterization and application in manufacturing of ZTA composites by gelcasting
Zhuang et al. Preparation and characterisation of phenolic foam/HTAB-ATP nanocomposites
Zhou et al. Scalable preparation of hollow polymer and carbon microspheres by spray drying and their application in low-density syntactic foam
Zhang et al. Large-sized graphene oxide as bonding agent for the liquid extrusion of nanoparticle aerogels
Wang et al. Influence of MCM-41 particle on mechanical and morphological behavior of polypropylene
CN103449406B (en) A kind of Powdered charcoal-aero gel and its preparation method and application
Pérez et al. Poly (methyl acrylate) plus mesoporous silica nanohybrids: mechanical and thermophysical properties
CN109984992A (en) Three-dimensional netted carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof
CN109985581A (en) Carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof
Zheng et al. Mechanochemical fabrication of geopolymer composites based on the reinforcement effect of microfibrillated cellulose
Yang et al. Preparation and characterization of clay aerogel composites reinforced by calcium sulfate whisker
Rangari et al. Size reduction of WO3 nanoparticles by ultrasound irradiation and its applications in structural nanocomposites
Gu et al. PCM microcapsules applicable foam to improve the properties of thermal insulation and energy storage for cement-based material
CN109985579A (en) Mesoporous-micropore carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20190709