CN109020472A - Mesoporous-micropore galapectite-silicon dioxide composite aerogel material and preparation method thereof - Google Patents
Mesoporous-micropore galapectite-silicon dioxide composite aerogel material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides mesoporous-micropore galapectite-silicon dioxide composite aerogel material and preparation method thereof, after galapectite dispersion liquid is polymerize with the mixed solution of dexamethasone, after ethyl orthosilicate, hydrochloric acid, gentamicin and initiator are added into polymerizate again, polymerization reaction is carried out again, sodium hydroxide is added in reaction process, and the reaction was continued, obtains mesoporous-micropore galapectite-silicon dioxide composite aerogel material.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
Technical field
The present invention relates to technical field of nano material, more specifically to a kind of mesoporous-micropore galapectite-titanium dioxide
Silicon compound aerogel material and preparation method thereof.
Background technique
Galapectite is natural one of clay mineral, belongs to kaolinic mutation, therefore also referred to as metakaolin.It is
It is crimped under field conditions (factors) by kaolinic lamella, main existence form is nanotube-shaped (Ma Zhi, king in nature
Gold leaf, Gao Xiang, Ding Tong, application study status [J] chemical progress of Qin Yongning halloysite nanotubes, 2012, (Z1): 275-
283.).Galapectite mine is distributed in each continent in the whole world, the countries such as China, France, Belgium, New Zealand, the U.S., Turkey
There are reserves abundant.Galapectite mine is mainly distributed on Guangdong, Hubei, Hunan, Sichuan, Guizhou, Yunnan, Shanxi etc. in China and saves
Part.
Galapectite is the double-deck 1:1 type aluminosilicate material, has typical crystalline texture.Galapectite is different from kaolinic
Substantive characteristics is that galapectite interlayer exists or once there is the crystallization water, and the lamella of galapectite is the oxygen-octahedron by outer layer
It is formed with the alumina octahedral regular array of internal layer, is free hydrone among lamella.These hydrones are easy to slough, this
Dehydration is irreversible.The outer surface of galapectite is mainly Si-O-Si key composition, and inner wall is then mainly aluminium hydroxyl (Niu Ji
South, Qiang Yinghuai, Wang Chunyang, Li Xiang, Monday is great, Shang Xiangyu, the village full the name of super galapectite, structure, pattern and curling mechanism
[J] mineral journal, 2014, (01): 13-22.).Silicon/aluminium hydroxyl is present on the crystallization edge of galapectite or the end face of pipe,
There is a small amount of embedding hydroxyl to be present in the inside of crystalline texture.Galapectite contains the water there are three types of state, mainly absorption water, crystallization
Water and chemical water.
Halloysite nanotubes have unique nanostructure, are a kind of natural nano-materials having a extensive future.And galapectite
Nanotube is widely distributed, cheap, nontoxic.Galapectite has following because of its unique nanostructure and tubular character
Advantage: firstly, it is from a wealth of sources, it is cheap；Galapectite is a kind of natural clay mineral, contains abundant, widely distributed and exploitation
It is easier to.Secondly, having good biocompatibility；Halloysite nanotubes self-assembling formation, nontoxic, biocompatibility is preferable.
In addition, active hydroxyl groups are contained in galapectite surface and interlayer, conducive to galapectite modification and further apply.Along with itself
Have the characteristics that biggish draw ratio and specific surface area, nanoscale, galapectite has obtained extensive concern and research in recent years.
The application field of halloysite nanotubes is extensive.In ceramic material, composite material, slow-release material, catalyst carrier, mould
Plate, adsorption applications etc. have a large amount of application.Because halloysite nanotubes are a kind of clay mines, it can be used for ceramic system
Make, this belongs to traditional application field of galapectite.Galapectite 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.Galapectite 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, (Wu Wei, Wu Pengjun, He Ding, Cao Xianwu, Zhou Nanqiao galapectite are received
Application progress [J] chemical industry progress of the mitron in high molecule nano composite material, 2011, (12): 2647-2651+2657.).
Galapectite has the characteristics that unique texture, environmental-friendly, cheap and easy to get, can prepare tool using its design feature and characterization of adsorption
There is the material of new structure and performance, 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 galapectite-compound gas of silica
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 galapectite-silicon dioxide composite aerogel material and preparation method thereof carries out as steps described below:
Step 1,0.5-20 parts by weight halloysite nanotubes are added to 50 parts by weight of deionized water and 50 parts by weight of ethanol
Mixed liquor in, ultrasonic disperse is uniform, obtain galapectite dispersion liquid, by 0.5-20 parts by weight of styrene sodium sulfonate, 0.05-5 weight
The poly- divinylsiloxanes of part, 0.01-0.5 parts by weight initiator are measured, 0.05-15 parts by weight dexamethasone is added to 50 parts by weight
In the mixed liquor of deionized water and 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after stirring, ultrasound point
After dissipating uniformly, vacuum is kept after vacuumizing, is then restored to normal pressure, after repeating vacuum step three times, is divided after product is washed
It dissipates in 100 parts by weight water, warming-in-water to initiated polymerization at 60-120 DEG C, polymerization reaction time is at least 48h, obtains
The product of step 1；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole hundred
Score (i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-
The poly dimethyl divinylsiloxanes of 5% amino list sealing end or the poly dimethyl divinyl silicon oxygen of amino bi-end-blocking
Alkane, poly- divinylsiloxanes are purchased from Dow corning company.
Step 2, it is scattered in after product being washed in 100 parts by weight water, 70-160 parts by weight ethyl orthosilicate is added,
0.05-2 parts by weight 12mol/L hydrochloric acid, the gentamicin of 0.01-2 parts by weight initiator and 0.05-20 parts by weight stir evenly
Afterwards, warming-in-water is then added 0.01-0.5 parts by weight of sodium hydroxide, stirs complete to its to initiated polymerization at 30-75 DEG C
After fully dissolved, polymerization reaction time is at least 48h, obtains mesoporous-micropore galapectite-compound wet gel of silica；
Initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
Step 3,0.05-2 parts by weight metering system is added in mesoporous-micropore galapectite-compound wet gel of silica
Acyloxy dodecyl trimethyl ammonium chloride, after standing, place the product in CO2In supercritical high-pressure extraction device, with CO2To be situated between
Matter carries out supercritical drying at least 1h at 30-60 DEG C of temperature and air pressure 5-15MPa, and mesoporous-micropore galapectite-two can be obtained
Silica aerogel composite.
In step 1, halloysite nanotubes are 1-15 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol ultrasonic
Disperse 1h, sodium styrene sulfonate is 1-15 parts by weight, and poly- divinylsiloxanes are 0.1-2 parts by weight, initiator 0.01-
0.1 parts by weight, dexamethasone are 0.1-10 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol and stir 20-60min
Afterwards, it is added in galapectite dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor.
In step 1, when carrying out polymerization reaction, selection polymerize 10-60min at 60-120 DEG C, is then cooled to 15-
It polymerize 12-24h at 50 DEG C, then successively polymerize 2-8h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
In step 2,80-150 parts by weight ethyl orthosilicate, 0.1-1 parts by weight 12mol/L are added into above-mentioned dispersion liquid
Hydrochloric acid, 0.01-1 parts by weight initiator and 0.1-15 parts by weight gentamicin stir 15-60min.
In step 2, when carrying out polymerization reaction, selection polymerize 15-40min at 30-75 DEG C, and 0.01-0.2 weight is added
Part sodium hydroxide is measured, stirring is completely dissolved to it, is then cooled in 20-50 DEG C of water bath with thermostatic control and polymerize 20-35h, then successively
It polymerize 2h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
In step 3, methacryloxy dodecyl trimethyl ammonium chloride is 0.1-1 parts by weight, and time of repose is
2-6h, the condition of supercritical drying are that supercritical drying 2-4h, preferably 3h are carried out at 33-50 DEG C of temperature and air pressure 7-10MPa.
Positive charge is had on the inside of halloysite nanotubes tube wall, and negative electrical charge, the styrene being added in step 1 are had on the outside of tube wall
Sodium sulfonate has negative electrical charge, and sodium styrene sulfonate is adsorbed on halloysite nanotubes inner wall by electrostatic interaction, while in step 1
Poly- divinylsiloxanes, initiator and the dexamethasone of middle addition are also dispersed in halloysite nanotubes hollow structure, Ai Luo
Stone nanotube hollow structure provides microcellular structure for mesoporous-micropore galapectite-silicon dioxide composite aerogel material, by taking out
After vacuum, washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed to be formed inside halloysite nanotubes and be handed over
It is coupled structure, dexamethasone is supported in halloysite nanotubes, step 2 to be located at poly- outside halloysite nanotubes hollow structure
Polymerize under the action of initiator between vinyl functional group in divinylsiloxanes so that halloysite nanotubes and
Tridimensional network is collectively formed in poly- divinylsiloxanes, and the ethyl orthosilicate being added in step 2, hydrochloric acid and sodium hydroxide are sent out
Raw reaction forms SiO2Particle, SiO2Particle is configured to network pore structure, above-mentioned tridimensional network and SiO2Particle building and
At network pore structure together form three-dimensional network pore structure, above-mentioned three-dimensional network pore structure is mesoporous-micropore angstrom
Lip river stone-silicon dioxide composite aerogel material provides meso-hole structure, while gentamicin being supported in meso-hole structure.
Using scientific and technological (Beijing) the Co., Ltd 3H-2000PS1 type static volumetric method specific surface area of Bei Shide instrument and aperture
The N of the tester analysis composite material that according to the present invention prepared by the method2Adsorption-desorption curve, such as Fig. 1.It can be with from figure
Find out, the N of the material2Adsorption-desorption curve is the IV class isothermal curve of H1 type hysteresis loop in IUPAC classification, i.e., by mesoporous knot
Structure generates.Illustrate that material itself has the pore structure of meso-scale.There is vertical ascent trend from the distribution of low pressure endpoint, can see
Sample interior is as caused by absorption potential strong inside micropore there are more micropore out.By nitrogen adsorption desorption isotherm data,
The sample specific surface area can reach 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=-0.963/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.363 [- 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
10.49nm, another kind are 2.47 μm, are measured through multiple groups, and nanoscale hole is average up to 10-12nm, and micro-meter scale hole is flat
Up to 2-4 μm.It can be seen that material exists simultaneously nanoscale and micro-meter scale hole.
Using the Nanosem430 field emission scanning electron microscope and Tecnai G2 F20 Flied emission of Dutch Philips
Transmission electron microscope observes the microscopic appearance of the composite material prepared using the method for the invention, as shown in Figure 2.
It can be seen from the figure that SiO2Particle is successfully configured to network pore structure, and aperture size is in mesoporous scale.It is overlapped to form three dimensional network
The halloysite nanotubes of shape are uniformly dispersed in SiO2In three-dimensional network hole, the building of dual load system is realized.
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, the drug celebrating being carried in mesoporous is big
Mycin takes the lead in discharging, and with further increasing for soaking time, the subsequent release of dexamethasone drug being carried in micropore is realized
Primary medication, the effect of multiple dosing.
Detailed description of the invention
Fig. 1 is mesoporous-micropore galapectite-silicon dioxide composite aerogel material N2Adsorption-desorption curve；
Fig. 2 is mesoporous-micropore galapectite-silicon dioxide composite aerogel material electromicroscopic photograph；
Fig. 3 is mesoporous-micropore galapectite-silicon dioxide composite aerogel material release product test curve；
Fig. 4 is mesoporous-micropore galapectite-silicon dioxide 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.
1 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 6 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.4 parts by weight
(number-average molecular weight 1000, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 4%),
0.01 parts by weight azodiisobutyronitrile (ABIN), 10 parts by weight dexamethasone are added to 50 parts by weight of deionized water and 50 parts by weight
In the mixed liquor of ethyl alcohol, 55min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, above-mentioned mixed liquor taken out true
1h is kept after sky, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 parts by weight are then dispersed in
In water, it is placed under 120 DEG C of water bath condition after prepolymerization 25min and polymerize 12 hours in 50 DEG C of water bath with thermostatic control, then by it
After successively polymerizeing 4h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 parts by weight water are scattered in after product is washed
In, 88 parts by weight ethyl orthosilicates, 0.9 parts by weight 12mol/L hydrochloric acid, 1 parts by weight azodiisobutyronitrile (ABIN) and 6 weights are added
Measure part gentamicin, at room temperature stir 45min after under 65 DEG C of water bath condition prepolymerization 40min, then be added 0.01 weight
Part sodium hydroxide is measured, stirring is completely dissolved to it, then polymerize 25 hours in 40 DEG C of water bath with thermostatic control, then it successively exists
80 DEG C, 90 DEG C, mesoporous-micropore galapectite-compound wet gel of silica is obtained after respectively placing 2h in 100 DEG C of water bath with thermostatic control,
0.4 parts by weight methacryloxy dodecyl front three is added in mesoporous-micropore galapectite-compound wet gel of silica
Ammonium chloride, after standing 4h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is gentle in temperature 50 C for medium
It presses and carries out supercritical drying 3h under 7MPa, mesoporous-micropore galapectite-silicon dioxide composite aerogel material can be obtained.
Embodiment 2.
15 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 10 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.1 parts by weight
(number-average molecular weight 3000, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 1%),
0.1 parts by weight azodiisobutyronitrile (ABIN), 5 parts by weight dexamethasone are added to 50 parts by weight of deionized water and 50 parts by weight second
In the mixed liquor of alcohol, 20min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min vacuumizes above-mentioned mixed liquor
After keep 1h, be then restored to normal pressure, after repeating vacuum step three times, product washed, 100 parts by weight water are then dispersed in
In, it is placed under 98 DEG C of water bath condition after prepolymerization 43min in 40 DEG C of water bath with thermostatic control and polymerize 19 hours, then successively by it
After polymerizeing 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, it is scattered in 100 parts by weight water, adds after product is washed
Enter 80 parts by weight ethyl orthosilicates, 0.5 parts by weight 12mol/L hydrochloric acid, 0.5 parts by weight azodiisobutyronitrile (ABIN) and 15 weight
Part gentamicin, at room temperature stir 15min after under 55 DEG C of water bath condition prepolymerization 28min, then be added 0.13 weight
Part sodium hydroxide, stirring are completely dissolved to it, then polymerize 20 hours in 50 DEG C of water bath with thermostatic control, then by it successively 80
DEG C, 90 DEG C, mesoporous-micropore galapectite-compound wet gel of silica is obtained after respectively placing 2h in 100 DEG C of water bath with thermostatic control,
0.2 parts by weight methacryloxy trimethyl is added in mesoporous-micropore galapectite-compound wet gel of silica
Ammonium chloride, after standing 5h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature 45 C and air pressure
Supercritical drying 3h is carried out under 8MPa, and mesoporous-micropore galapectite-silicon dioxide composite aerogel material can be obtained.
Embodiment 3.
8 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 15 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.8 parts by weight
(number-average molecular weight 2000, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 3%),
0.08 parts by weight azodiisobutyronitrile (ABIN), 3 parts by weight dexamethasone are added to 50 parts by weight of deionized water and 50 parts by weight
In the mixed liquor of ethyl alcohol, 52min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, above-mentioned mixed liquor taken out true
1h is kept after sky, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 parts by weight are then dispersed in
In water, be placed under 60 DEG C of water bath condition after prepolymerization 10min in 30 DEG C of water bath with thermostatic control and polymerize 18 hours, then by its according to
It is secondary polymerize 5h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control after, be scattered in after product is washed in 100 parts by weight water,
150 parts by weight ethyl orthosilicates, 0.1 parts by weight 12mol/L hydrochloric acid, 0.9 parts by weight azodiisobutyronitrile (ABIN) and 4 weights are added
Measure part gentamicin, at room temperature stir 30min after under 66 DEG C of water bath condition prepolymerization 20min, then be added 0.19 weight
Part sodium hydroxide is measured, stirring is completely dissolved to it, and then polyase 13 0 hour in 30 DEG C of water bath with thermostatic control, then successively exists it
80 DEG C, 90 DEG C, mesoporous-micropore galapectite-compound wet gel of silica is obtained after respectively placing 2h in 100 DEG C of water bath with thermostatic control,
1 parts by weight methacryloxy trimethyl is added in mesoporous-micropore galapectite-compound wet gel of silica
Ammonium chloride, after standing 2h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 38 DEG C of temperature and air pressure
Supercritical drying 3h is carried out under 8.5MPa, and mesoporous-micropore galapectite-silicon dioxide composite aerogel material can be obtained.
Embodiment 4.
3 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 5 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.9 parts by weight
(number-average molecular weight 2500, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 3%),
0.04 parts by weight azodiisobutyronitrile (ABIN), 8 parts by weight dexamethasone are added to 50 parts by weight of deionized water and 50 parts by weight
In the mixed liquor of ethyl alcohol, 60min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, above-mentioned mixed liquor taken out true
1h is kept after sky, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 parts by weight are then dispersed in
In water, be placed under 85 DEG C of water bath condition after prepolymerization 19min in 25 DEG C of water bath with thermostatic control and polymerize 15 hours, then by its according to
It is secondary in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control distinguish polyase 13 h after, be scattered in after product is washed in 100 parts by weight water,
90 parts by weight ethyl orthosilicates, 1 parts by weight 12mol/L hydrochloric acid, 0.3 parts by weight azodiisobutyronitrile (ABIN) and 7 weight are added
Part gentamicin, at room temperature stir 55min after under 75 DEG C of water bath condition prepolymerization 15min, then be added 0.02 weight
Part sodium hydroxide, stirring are completely dissolved to it, then polymerize 28 hours in 45 DEG C of water bath with thermostatic control, then by it successively 80
DEG C, 90 DEG C, mesoporous-micropore galapectite-compound wet gel of silica is obtained after respectively placing 2h in 100 DEG C of water bath with thermostatic control,
0.7 parts by weight methacryloxy trimethyl is added in mesoporous-micropore galapectite-compound wet gel of silica
Ammonium chloride, after standing 3h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 43 DEG C of temperature and air pressure
Supercritical drying 3h is carried out under 7.5MPa, and mesoporous-micropore galapectite-silicon dioxide composite aerogel material can be obtained.
Embodiment 5.
4 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 3 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 1.4 parts by weight
(number-average molecular weight 1500, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 4%),
0.05 parts by weight dibenzoyl peroxide (BPO), 0.1 parts by weight dexamethasone are added to 50 parts by weight of deionized water and 50 weight
In the mixed liquor of part ethyl alcohol, 35min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min takes out above-mentioned mixed liquor
1h is kept after vacuum, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 weight are then dispersed in
It in part water, is placed under 110 DEG C of water bath condition after prepolymerization 31min and polymerize 24 hours in 35 DEG C of water bath with thermostatic control, then will
After it successively polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 parts by weight water are scattered in after product is washed
In, be added 89 parts by weight ethyl orthosilicates, 0.7 parts by weight 12mol/L hydrochloric acid, 0.1 parts by weight dibenzoyl peroxide (BPO) and
The gentamicin of 0.1 parts by weight stirs prepolymerization 33min, then addition under 44 DEG C of water bath condition after 41min at room temperature
0.2 parts by weight of sodium hydroxide, stirring are completely dissolved to it, then polymerize 26 hours in 20 DEG C of water bath with thermostatic control, then by it
Successively respectively place that obtain mesoporous-micropore galapectite-silica after 2h compound wet in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
0.8 parts by weight methacryloxy dodecane is added in gel in mesoporous-micropore galapectite-compound wet gel of silica
Base trimethyl ammonium chloride, after standing 6h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature 33
DEG C and air pressure 10MPa under carry out supercritical drying 3h, mesoporous-micropore galapectite-silicon dioxide composite aerogel material can be obtained
Material.
Embodiment 6.
9 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 1 parts by weight of styrene sodium sulfonate, the poly- divinylsiloxanes of 1.8 parts by weight
(number-average molecular weight 5000, the poly dimethyl divinyl silicon oxygen of the amino bi-end-blocking of contents of ethylene mole percent 0.1%
Alkane), 0.07 parts by weight dibenzoyl peroxide (BPO), 4 parts by weight dexamethasone are added to 50 parts by weight of deionized water and 50 weights
In the mixed liquor for measuring part ethyl alcohol, 44min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, by above-mentioned mixed liquor
1h is kept after vacuumizing, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 weights are then dispersed in
It measures in part water, is placed under 80 DEG C of water bath condition after prepolymerization 60min and polymerize 20 hours in 15 DEG C of water bath with thermostatic control, then will
After it successively polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 parts by weight water are scattered in after product is washed
In, be added 87 parts by weight ethyl orthosilicates, 0.8 parts by weight 12mol/L hydrochloric acid, 0.8 parts by weight dibenzoyl peroxide (BPO) and
The gentamicin of 5 parts by weight, at room temperature stir 60min after under 30 DEG C of water bath condition prepolymerization 25min, be then added 0.18
Parts by weight of sodium hydroxide is stirred to it and is completely dissolved, then polyase 13 5 hours in 35 DEG C of water bath with thermostatic control, then successively by it
Respectively place that mesoporous-micropore galapectite-silica is obtained after 2h is compound wet solidifying in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
0.1 parts by weight methacryloxy dodecyl is added in glue in mesoporous-micropore galapectite-compound wet gel of silica
Trimethyl ammonium chloride, after standing 3.5h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature 39
DEG C and air pressure 9MPa under carry out supercritical drying 3h, mesoporous-micropore galapectite-silicon dioxide composite aerogel material can be obtained
Material.
Embodiment 7
20 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 20 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 5 parts by weight (number
Average molecular weight 500, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 5%), 0.5
Parts by weight dibenzoyl peroxide (BPO), 15 parts by weight dexamethasone are added to 50 parts by weight of deionized water and 50 parts by weight second
In the mixed liquor of alcohol, 60min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min vacuumizes above-mentioned mixed liquor
After keep 1h, be then restored to normal pressure, after repeating vacuum step three times, product washed, 100 parts by weight water are then dispersed in
In, it is placed under 85 DEG C of water bath condition after prepolymerization 19min in 25 DEG C of water bath with thermostatic control and polymerize 15 hours, then successively by it
After distinguishing polyase 13 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, it is scattered in 100 parts by weight water, adds after product is washed
Enter 160 parts by weight ethyl orthosilicates, 2 parts by weight 12mol/L hydrochloric acid, 2 parts by weight dibenzoyl peroxides (BPO) and 20 parts by weight
Gentamicin, at room temperature stir 55min after under 75 DEG C of water bath condition prepolymerization 15min, then be added 0.5 parts by weight hydrogen
Sodium oxide molybdena, stirring is completely dissolved to it, then polymerize in 45 DEG C of water bath with thermostatic control 28 hours, then by it successively at 80 DEG C,
90 DEG C, mesoporous-micropore galapectite-compound wet gel of silica is obtained after respectively placing 2h in 100 DEG C of water bath with thermostatic control, is being situated between
2 parts by weight methacryloxy trimethyl chlorinations are added in hole-micropore galapectite-compound wet gel of silica
Ammonium, after standing 3h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 30 DEG C of temperature and air pressure 5MPa
Lower progress supercritical drying 4h, can be obtained mesoporous-micropore galapectite-silicon dioxide composite aerogel material.
Embodiment 8
0.5 parts by weight halloysite nanotubes are added to the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol
In, ultrasonic disperse 1h obtains galapectite dispersion liquid, by 0.5 parts by weight of styrene sodium sulfonate, the poly- divinyl silicon of 0.05 parts by weight
Oxygen alkane (number-average molecular weight 4500, the poly dimethyl divinyl silicon of the amino list sealing end of contents of ethylene mole percent 0.5%
Oxygen alkane), 0.01 parts by weight dibenzoyl peroxide (BPO), 0.05 parts by weight dexamethasone is added to 50 parts by weight of deionized water
In the mixed liquor of 50 parts by weight of ethanol, 44min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min will be above-mentioned
Mixed liquor keeps 1h after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, product is washed, is then dispersed
In 100 parts by weight water, it is small that in 15 DEG C of water bath with thermostatic control polymerization 20 is placed under 80 DEG C of water bath condition after prepolymerization 60min
When, after it is successively then polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, it is scattered in after product is washed
In 100 parts by weight water, 70 parts by weight ethyl orthosilicates, 0.05 parts by weight 12mol/L hydrochloric acid, 0.01 parts by weight peroxidating two is added
The gentamicin of benzoyl (BPO) and 0.05 parts by weight stir the prepolymerization under 30 DEG C of water bath condition after 60min at room temperature
25min, is then added 0.01 parts by weight of sodium hydroxide, and stirring is completely dissolved to it, then polymerize in 35 DEG C of water bath with thermostatic control
35 hours, mesoporous-micropore angstrom Lip river was obtained after it is successively respectively then placed 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
0.05 parts by weight first is added in mesoporous-micropore galapectite-compound wet gel of silica in the compound wet gel of stone-silica
Base acryloxy dodecyl trimethyl ammonium chloride, after standing 3.5h, place the product in CO2Supercritical high-pressure extraction device
In, with CO2Supercritical drying 2h is carried out under temperature 60 C and air pressure 15MPa for medium, and mesoporous-micropore angstrom Lip river can be obtained
Stone-silicon dioxide composite aerogel material.
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 galapectite-silicon dioxide composite aerogel material, it is characterised in that: the compound gas of galapectite-silica
Gel rubber material average specific surface area is 600-608m2g-1, nanometer is existed simultaneously in galapectite-silicon dioxide composite aerogel material
Scale and micro-meter scale hole, nanoscale hole average out to 10-12nm, 2-4 μm of average out to of micro-meter scale hole, according to following
Step carries out:
Step 1,0.5-20 parts by weight halloysite nanotubes are added to the mixed of 50 parts by weight of deionized water and 50 parts by weight of ethanol
It closes in liquid, ultrasonic disperse is uniform, galapectite dispersion liquid is obtained, by 0.5-20 parts by weight of styrene sodium sulfonate, 0.05-5 parts by weight
Poly- divinylsiloxanes, 0.01-0.5 parts by weight initiator, 0.05-15 parts by weight dexamethasone be added to 50 parts by weight go from
In sub- water and the mixed liquor of 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after stirring, ultrasonic disperse is equal
After even, vacuum is kept after vacuumizing, is then restored to normal pressure, after repeating vacuum step three times, is scattered in after product is washed
In 100 parts by weight water, warming-in-water to initiated polymerization at 60-120 DEG C, polymerization reaction time is at least 48h, obtains step
1 product；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole percent
(i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-5%'s
The poly dimethyl divinylsiloxanes of amino list sealing end or the poly dimethyl divinylsiloxanes of amino bi-end-blocking；
Step 2, it is scattered in after product being washed in 100 parts by weight water, 70-160 parts by weight ethyl orthosilicate, 0.05-2 weight is added
Amount part 12mol/L hydrochloric acid, the gentamicin of 0.01-2 parts by weight initiator and 0.05-20 parts by weight, after mixing evenly, water-bath liter
Temperature to initiated polymerization at 30-75 DEG C, subsequent addition 0.01-0.5 parts by weight of sodium hydroxide stirs after being completely dissolved to it,
Polymerization reaction time is at least 48h, obtains mesoporous-micropore galapectite-compound wet gel of silica；
Step 3,0.05-2 parts by weight methacryloxypropyl is added in mesoporous-micropore galapectite-compound wet gel of silica
Base dodecyl trimethyl ammonium chloride, after standing, place the product in CO2In supercritical high-pressure extraction device, with CO2Exist for medium
Supercritical drying at least 1h is carried out under 30-60 DEG C of temperature and air pressure 5-15MPa, mesoporous-micropore galapectite-titanium dioxide can be obtained
Silicon compound aerogel material；
Positive charge is had on the inside of halloysite nanotubes tube wall, and negative electrical charge, the styrene sulfonic acid being added in step 1 are had on the outside of tube wall
Sodium has negative electrical charge, and sodium styrene sulfonate is adsorbed on halloysite nanotubes inner wall by electrostatic interaction, while adding in step 1
Poly- divinylsiloxanes, initiator and the dexamethasone entered is also dispersed in halloysite nanotubes hollow structure, and galapectite is received
Mitron hollow structure provides microcellular structure for mesoporous-micropore galapectite-silicon dioxide composite aerogel material, true by taking out
After empty, washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed crosslinking inside halloysite nanotubes
Dexamethasone is supported in halloysite nanotubes by structure, and step 2 makes be located at outside halloysite nanotubes hollow structure poly- two
It polymerize under the action of initiator between vinyl functional group on vinylsiloxane, so that halloysite nanotubes and poly-
Tridimensional network is collectively formed in divinylsiloxanes, and the ethyl orthosilicate being added in step 2, hydrochloric acid and sodium hydroxide occur
Reaction forms SiO2Particle, SiO2Particle is configured to network pore structure, above-mentioned tridimensional network and SiO2Particle is built-up
Network pore structure together form three-dimensional network pore structure, above-mentioned three-dimensional network pore structure is mesoporous-micropore angstrom Lip river
Stone-silicon dioxide composite aerogel material provides meso-hole structure, while gentamicin being supported in meso-hole structure.
2. mesoporous-micropore galapectite-silicon dioxide composite aerogel material according to claim 1, it is characterised in that:
In step 1, halloysite nanotubes are 1-15 parts by weight, are added to ultrasonic disperse 1h, benzene in the mixed liquor of deionized water and ethyl alcohol
Vinyl sulfonic acid sodium is 1-15 parts by weight, and poly- divinylsiloxanes are 0.1-2 parts by weight, and initiator is 0.01-0.1 parts by weight,
Dexamethasone is 0.1-10 parts by weight, is added to after stirring 20-60min in the mixed liquor of deionized water and ethyl alcohol, is added to angstrom
In the stone dispersion liquid of Lip river, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, and when carrying out polymerization reaction, selection exists
It polymerize 10-60min at 60-120 DEG C, is then cooled at 15-50 DEG C and polymerize 12-24h, then successively at 80 DEG C, 90 DEG C and 100 DEG C
It is lower to polymerize 2-8h respectively.
3. mesoporous-micropore galapectite-silicon dioxide composite aerogel material according to claim 1, it is characterised in that:
In step 2,80-150 parts by weight ethyl orthosilicate, 0.1-1 parts by weight 12mol/L hydrochloric acid, 0.01- are added into above-mentioned dispersion liquid
1 parts by weight initiator and 0.1-15 parts by weight gentamicin stir 15-60min, and when carrying out polymerization reaction, selection is at 30-75 DEG C
0.01-0.2 parts by weight of sodium hydroxide is added in lower polymerization 15-40min, and stirring is completely dissolved to it, is then cooled to 20-50 DEG C
Water bath with thermostatic control in polymerize 20-35h, then successively polymerize 2h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
4. mesoporous-micropore galapectite-silicon dioxide composite aerogel material according to claim 1, it is characterised in that: draw
Send out agent selection dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
5. mesoporous-micropore galapectite-silicon dioxide composite aerogel material according to claim 1, it is characterised in that:
In step 3, methacryloxy dodecyl trimethyl ammonium chloride is 0.1-1 parts by weight, and time of repose 2-6h is overcritical
Dry condition is that supercritical drying 2-4h, preferably 3h are carried out at 33-50 DEG C of temperature and air pressure 7-10MPa.
6. preparing mesoporous-micropore galapectite-silicon dioxide composite aerogel material side as claimed in claim 1 to 5
Method, it is characterised in that: carry out as steps described below:
Step 1,0.5-20 parts by weight halloysite nanotubes are added to the mixed of 50 parts by weight of deionized water and 50 parts by weight of ethanol
It closes in liquid, ultrasonic disperse is uniform, galapectite dispersion liquid is obtained, by 0.5-20 parts by weight of styrene sodium sulfonate, 0.05-5 parts by weight
Poly- divinylsiloxanes, 0.01-0.5 parts by weight initiator, 0.05-15 parts by weight dexamethasone be added to 50 parts by weight go from
In sub- water and the mixed liquor of 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after stirring, ultrasonic disperse is equal
After even, vacuum is kept after vacuumizing, is then restored to normal pressure, after repeating vacuum step three times, is scattered in after product is washed
In 100 parts by weight water, warming-in-water to initiated polymerization at 60-120 DEG C, polymerization reaction time is at least 48h, obtains step
1 product；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole percent
(i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-5%'s
The poly dimethyl divinylsiloxanes of amino list sealing end or the poly dimethyl divinylsiloxanes of amino bi-end-blocking；
Step 2, it is scattered in after product being washed in 100 parts by weight water, 70-160 parts by weight ethyl orthosilicate, 0.05-2 weight is added
Amount part 12mol/L hydrochloric acid, the gentamicin of 0.01-2 parts by weight initiator and 0.05-20 parts by weight, after mixing evenly, water-bath liter
Temperature to initiated polymerization at 30-75 DEG C, subsequent addition 0.01-0.5 parts by weight of sodium hydroxide stirs after being completely dissolved to it,
Polymerization reaction time is at least 48h, obtains mesoporous-micropore galapectite-compound wet gel of silica；
Step 3,0.05-2 parts by weight methacryloxypropyl is added in mesoporous-micropore galapectite-compound wet gel of silica
Base dodecyl trimethyl ammonium chloride, after standing, place the product in CO2In supercritical high-pressure extraction device, with CO2Exist for medium
Supercritical drying at least 1h is carried out under 30-60 DEG C of temperature and air pressure 5-15MPa, mesoporous-micropore galapectite-titanium dioxide can be obtained
Silicon compound aerogel material；
Positive charge is had on the inside of halloysite nanotubes tube wall, and negative electrical charge, the styrene sulfonic acid being added in step 1 are had on the outside of tube wall
Sodium has negative electrical charge, and sodium styrene sulfonate is adsorbed on halloysite nanotubes inner wall by electrostatic interaction, while adding in step 1
Poly- divinylsiloxanes, initiator and the dexamethasone entered is also dispersed in halloysite nanotubes hollow structure, and galapectite is received
Mitron hollow structure provides microcellular structure for mesoporous-micropore galapectite-silicon dioxide composite aerogel material, true by taking out
After empty, washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed crosslinking inside halloysite nanotubes
Dexamethasone is supported in halloysite nanotubes by structure, and step 2 makes be located at outside halloysite nanotubes hollow structure poly- two
It polymerize under the action of initiator between vinyl functional group on vinylsiloxane, so that halloysite nanotubes and poly-
Tridimensional network is collectively formed in divinylsiloxanes, and the ethyl orthosilicate being added in step 2, hydrochloric acid and sodium hydroxide occur
Reaction forms SiO2Particle, SiO2Particle is configured to network pore structure, above-mentioned tridimensional network and SiO2Particle is built-up
Network pore structure together form three-dimensional network pore structure, above-mentioned three-dimensional network pore structure is mesoporous-micropore angstrom Lip river
Stone-silicon dioxide composite aerogel material provides meso-hole structure, while gentamicin being supported in meso-hole structure.
7. mesoporous-micropore galapectite-silicon dioxide composite aerogel material preparation method according to claim 6,
Be characterized in that: in step 1, halloysite nanotubes are 1-15 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol and surpass
Sound disperses 1h, and sodium styrene sulfonate is 1-15 parts by weight, and poly- divinylsiloxanes are 0.1-2 parts by weight, initiator 0.01-
0.1 parts by weight, dexamethasone are 0.1-10 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol and stir 20-60min
Afterwards, it is added in galapectite dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, anti-polymerize
Seasonable selection polymerize 10-60min at 60-120 DEG C, is then cooled at 15-50 DEG C and polymerize 12-24h, then successively at 80 DEG C,
It polymerize 2-8h respectively at 90 DEG C and 100 DEG C.
8. mesoporous-micropore galapectite-silicon dioxide composite aerogel material preparation method according to claim 6,
It is characterized in that: in step 2,80-150 parts by weight ethyl orthosilicate, 0.1-1 parts by weight 12mol/ being added into above-mentioned dispersion liquid
L hydrochloric acid, 0.01-1 parts by weight initiator and 0.1-15 parts by weight gentamicin stir 15-60min, the choosing when carrying out polymerization reaction
It selects and polymerize 15-40min at 30-75 DEG C, 0.01-0.2 parts by weight of sodium hydroxide is added, stirring is completely dissolved to it, then drops
Temperature polymerize 20-35h into 20-50 DEG C of water bath with thermostatic control, then successively polymerize 2h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
9. mesoporous-micropore galapectite-silicon dioxide composite aerogel material preparation method according to claim 6,
Be characterized in that: initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
10. mesoporous-micropore galapectite-silicon dioxide composite aerogel material preparation method according to claim 6,
Be characterized in that: in step 3, methacryloxy dodecyl trimethyl ammonium chloride is 0.1-1 parts by weight, and time of repose is
2-6h, the condition of supercritical drying are that supercritical drying 2-4h, preferably 3h are carried out at 33-50 DEG C of temperature and air pressure 7-10MPa.
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