CN108976360A - Three-dimensional netted galapectite aerogel material and preparation method thereof - Google Patents
Three-dimensional netted galapectite aerogel material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides three-dimensional netted galapectite aerogel material and preparation method thereof, after galapectite dispersion liquid is polymerize with the mixed solution of frusemide, after adding nitre benzene arsenic heavy stone used as an anchor and initiator into polymerizate again, polymerization reaction is carried out again, obtains three-dimensional netted galapectite aerogel material.The beneficial effects of the invention are as follows gradually increasing with soaking time, the drug nitre benzene arsenic heavy stone used as an anchor being carried in mesoporous takes the lead in discharging, with further increasing for soaking time, the subsequent release of frusemide drug that is carried in micropore, realize primary medication, the effect of multiple dosing.
Description
Technical field
The invention belongs to technical field of nano material, more particularly, are related to a kind of three-dimensional netted galapectite aeroge
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 deficiency in the prior art, provide a kind of mesoporous-micropore galapectite aerogel material and its
Preparation method uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilizes the mesoporous of aeroge
The microcellular structure of structure and fiber, loads different pharmaceutical respectively, realizes the ladder-like classification release of drug.
The purpose of the present invention is achieved by following technical proposals.
Three-dimensional netted galapectite aerogel material and preparation method thereof carries out as steps described below:
Step 1,0.1-20 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, obtains galapectite dispersion liquid；By 0.1-20 parts by weight of styrene sodium sulfonate, 0.01-2 weight
The poly- divinylsiloxanes of part, 0.01-0.5 parts by weight initiator are measured, 0.05-10 parts by weight frusemide is added to 50 parts by weight and goes
In ionized 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
Uniformly, vacuum is kept after vacuumizing, is restored to normal pressure, and after repetition vacuumizes three times, washing obtains step 1 product；
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 is purchased from Dow corning company.
Step 2, it disperses step 1 product in 100 parts by weight water, warming-in-water to 50-80 DEG C of initiated polymerization, gathers
The conjunction reaction time is at least 48h, obtains step 2 product；
Step 3, it will be scattered in 100 parts by weight water after the washing of step 2 product, the nitre benzene arsenic of 0.05-20 parts by weight be added
Heavy stone used as an anchor and 0.01-2 parts by weight initiator, after mixing evenly, warming-in-water to 60-100 DEG C of initiated polymerization, polymerization reaction time
Three-dimensional netted galapectite hydrogel is made at least 36h；
Step 4, three-dimensional netted galapectite hydrogel is placed in CO2In supercritical high-pressure extraction device, with CO2Exist for medium
Supercritical drying at least 1h is carried out under 10-300 DEG C of temperature and air pressure 1-20MPa, three-dimensional netted galapectite airsetting glue material can be obtained
Material.
Initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
In step 1, halloysite nanotubes are 1-10 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol ultrasonic
Disperse 1h, sodium styrene sulfonate is 1-10 parts by weight, and poly- divinylsiloxanes are 0.1-1 parts by weight, initiator 0.01-
0.1 parts by weight, frusemide are 0.1-5 parts by weight, are added to after stirring 10-60min in the mixed liquor of deionized water and ethyl alcohol, add
Enter into galapectite dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor.
In step 2, selection polyase 13 0-60min at 50-80 DEG C when carrying out polymerization reaction, is then cooled to 10-60
It polymerize 12-24h at DEG C, then successively polymerize 2-8h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
In step 3,0.1-15 parts by weight nitre benzene arsenic heavy stone used as an anchor and 0.01-1 parts by weight initiator are added into above-mentioned dispersion liquid
Stir 1h.
In step 3, when carrying out polymerization reaction, selection polymerize 20-50min at 60-100 DEG C, is then cooled to 30-
It polymerize 20-30h at 70 DEG C, then successively polymerize 2h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
In step 4, the time for carrying out supercritical drying is 2-4h, preferably 3h.
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 frusemide of middle addition are also dispersed in halloysite nanotubes hollow structure, galapectite
Nanotube hollow structure provides microcellular structure for three-dimensional netted galapectite aerogel material, by vacuumizing, washing, in step
Poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate in 2, are formed and are formed cross-linked structure inside halloysite nanotubes, will
Frusemide is supported in halloysite nanotubes, and step 3 makes the poly- divinyl silicon being located at outside halloysite nanotubes hollow structure
It polymerize under the action of initiator between vinyl functional group on oxygen alkane, so that halloysite nanotubes and poly- divinyl
Tridimensional network is collectively formed in siloxanes, and above-mentioned tridimensional network provides mesoporous for three-dimensional netted galapectite aerogel material
Structure, while nitre benzene arsenic heavy stone used as an anchor 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 N2 adsorption-desorption curve of the tester analysis composite material that according to the present invention prepared by the method, 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
Average specific surface area is measured up to 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=-0.943/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.384 [- 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
10.55nm, another kind are 20.58 μm, and average up to 10-12nm through multiple groups measurement nanoscale hole, 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 the success of halloysite nanotubes fiber
It is configured to network pore structure, aperture size is in mesoporous scale.In conjunction with halloysite nanotubes inner wall microcellular structure, realize double
The building of heavy duty system.
Reference literature (Li Degui, the preparation and characterization of nano-cellulose base Thermosensitive Material Used for Controlled Releasing of Medicine, South China Science & Engineering University,
2016) method described in carries out sustained release performance test characterization to material prepared by the present invention.Two sustained release steps are delayed respectively
It releases product and carries out infrared spectroscopy detection, as a result as shown in figure 3, by being compareed with standard diagram, it was demonstrated that take the lead in release is nitre benzene
Pyridine, what is then discharged is frusemide, realizes the multiple dimensioned load and repeatedly release of different pharmaceutical.
The composite material carrying medicament prepared using the method for the invention is placed in simulation human consumption's liquid, measurement
Its drug release effect, figure 4, it is seen that gradually increasing with soaking time, the drug nitre benzene being carried in mesoporous
Arsenic heavy stone used as an anchor takes the lead in discharging, and with further increasing for soaking time, the subsequent release of frusemide drug being carried in micropore is realized
Primary medication, the effect of multiple dosing.
Detailed description of the invention
Fig. 1 is the N of three-dimensional netted galapectite aerogel material2Adsorption-desorption curve；
Fig. 2 is the electromicroscopic photograph of three-dimensional netted galapectite aerogel material；
Fig. 3 is the release product test curve of three-dimensional netted galapectite aerogel material；
Fig. 4 is the carrying medicament release profiles of three-dimensional netted galapectite aerogel material.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1.
5 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 0.3 parts by weight
(number-average molecular weight 5000, the poly dimethyl divinyl silicon oxygen of the amino list sealing end of contents of ethylene mole percent 0.1%
Alkane), 0.07 parts by weight aoxidize dibenzoyl (BPO), and 3 parts by weight frusemides are added to 50 parts by weight of deionized water and 50 parts by weight
In the mixed liquor of ethyl alcohol, 50min 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 70 DEG C of water bath condition after prepolymerization 24min in 20 DEG C of water bath with thermostatic control and polymerize 19 hours, then by its according to
It is secondary that polyase 13 h is distinguished 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 nitre benzene arsenic heavy stone used as an anchor and 0.3 parts by weight oxidation dibenzoyl (BPO) of 9 parts by weight, stirring 1h is placed under 100 DEG C of water bath condition
Then prepolymerization 40min polymerize 24 hours in 56 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C
Three-dimensional netted galapectite hydrogel is made after polymerizeing 2h in water bath with thermostatic control respectively, place the product in CO2Supercritical, high pressure extraction dress
In setting, with CO2Supercritical drying 3h is carried out at 20 DEG C of temperature and air pressure 12MPa for medium, and three-dimensional netted galapectite can be obtained
Aerogel material.
Embodiment 2.
7 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 0.5 parts by weight
(number-average molecular weight 500, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 5%),
0.01 parts by weight azodiisobutyronitrile (ABIN), 5 parts by weight frusemides are added to 50 parts by weight of deionized water and 50 parts by weight second
In the mixed liquor of alcohol, 11min 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 75 DEG C of water bath condition after prepolymerization 35min in 60 DEG C of water bath with thermostatic control and polymerize 12 hours, then successively by it
It polymerize 5h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, is scattered in after product is washed in 100 parts by weight water, is added 5
The nitre benzene arsenic heavy stone used as an anchor of parts by weight and 0.5 parts by weight azodiisobutyronitrile (ABIN), stirring 1h are placed under 85 DEG C of water bath condition in advance
It polymerize 48min, then polymerize 28 hours in 40 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C of perseverance
Three-dimensional netted galapectite hydrogel is made after polymerizeing 2h in tepidarium respectively, place the product in CO2Supercritical high-pressure extraction device
In, with CO2Supercritical drying 3h is carried out at 10 DEG C of temperature and air pressure 14MPa for medium, and three-dimensional netted galapectite gas can be obtained
Gel rubber material.
Embodiment 3.
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 4 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.8 parts by weight
(number-average molecular weight 1000, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 4%),
0.1 parts by weight azodiisobutyronitrile (ABIN), 0.7 parts by weight frusemide are added to 50 parts by weight of deionized water and 50 parts by weight second
In the mixed liquor of alcohol, 13min 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 50 DEG C of water bath condition after prepolymerization 30min in 10 DEG C of water bath with thermostatic control and polymerize 18 hours, then successively by it
It polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, is scattered in after product is washed in 100 parts by weight water, is added
The nitre benzene arsenic heavy stone used as an anchor of 0.1 parts by weight and 0.7 parts by weight azodiisobutyronitrile (ABIN), stirring 1h are placed under 90 DEG C of water bath condition
Prepolymerization 35min, then polyase 13 0 hour in 30 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C
Three-dimensional netted galapectite hydrogel is made after polymerizeing 2h in water bath with thermostatic control respectively, place the product in CO2Supercritical, high pressure extraction dress
In setting, with CO2Supercritical drying 3h is carried out at 100 DEG C of temperature and air pressure 3MPa for medium, and three-dimensional netted galapectite can be obtained
Aerogel material.
Embodiment 4.
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 0.7 parts by weight
(number-average molecular weight 3000, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 1%),
0.03 parts by weight aoxidize dibenzoyl (BPO), and 0.1 parts by weight frusemide is 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 55 DEG C of water bath condition after prepolymerization 60min in 55 DEG C of water bath with thermostatic control and polymerize 24 hours, then successively by it
It polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, is scattered in after product is washed in 100 parts by weight water, is added 4
The nitre benzene arsenic heavy stone used as an anchor of parts by weight and 0.8 parts by weight oxidation dibenzoyl (BPO), stirring 1h are placed on pre-polymerization under 80 DEG C of water bath condition
39min is closed, then polymerize 20 hours in 37 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C of constant temperature
Three-dimensional netted galapectite hydrogel is made after polymerizeing 2h in water-bath respectively, place the product in CO2In supercritical high-pressure extraction device,
With CO2Supercritical drying 3h is carried out at 300 DEG C of temperature and air pressure 5MPa for medium, and three-dimensional netted galapectite aeroge can be obtained
Material.
Embodiment 5.
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 2 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 1 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%),
0.02 parts by weight aoxidize dibenzoyl (BPO), and 0.8 parts by weight frusemide is 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 60 DEG C of water bath condition after prepolymerization 20min in 19 DEG C of water bath with thermostatic control and polymerize 15 hours, then successively by it
It polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, is scattered in after product is washed in 100 parts by weight water, is added
The nitre benzene arsenic heavy stone used as an anchor of 15 parts by weight and 0.01 parts by weight oxidation dibenzoyl (BPO), stirring 1h are placed under 60 DEG C of water bath condition
Then prepolymerization 20min polymerize 27 hours in 70 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C
Three-dimensional netted galapectite hydrogel is made after polymerizeing 2h in water bath with thermostatic control respectively, place the product in CO2Supercritical, high pressure extraction dress
In setting, with CO2Supercritical drying 3h is carried out at 150 DEG C of temperature and air pressure 20MPa for medium, and three-dimensional netted galapectite can be obtained
Aerogel material.
Embodiment 6.
10 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 8 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.1 parts by weight
(number-average molecular weight 4000, the poly dimethyl divinyl silicon oxygen of the amino bi-end-blocking of contents of ethylene mole percent 0.5%
Alkane), 0.05 parts by weight azodiisobutyronitrile (ABIN), 0.3 parts by weight frusemide is added to 50 parts by weight of deionized water and 50 weights
In the mixed liquor for measuring part ethyl alcohol, 10min 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 37min and polymerize 20 hours in 50 DEG C of water bath with thermostatic control, then will
It successively polymerize 4h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively, and 100 parts by weight water are scattered in after product is washed
In, the nitre benzene arsenic heavy stone used as an anchor and 1 parts by weight azodiisobutyronitrile (ABIN) of 6 parts by weight is added, stirring 1h is placed on 75 DEG C of water-bath item
Then prepolymerization 50min under part polymerize 25 hours, then by it successively at 80 DEG C, 90 DEG C, 100 in 45 DEG C of water bath with thermostatic control
DEG C water bath with thermostatic control in polymerize 2h respectively after three-dimensional netted galapectite hydrogel is made, place the product in CO2Supercritical, high pressure extraction
It takes in device, with CO2Supercritical drying 3h is carried out at 55 DEG C of temperature and air pressure 1MPa for medium, and three-dimensional netted angstrom of Lip river can be obtained
Stone aerogel material.
Embodiment 7
0.1 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 0.1 parts by weight of styrene sodium sulfonate, the poly- divinyl silicon of 0.01 parts by weight
Oxygen alkane (number-average molecular weight 3500, the poly dimethyl divinyl silicon oxygen of the amino list sealing end of contents of ethylene mole percent 3%
Alkane), 0.01 parts by weight azodiisobutyronitrile (ABIN), 0.05 parts by weight frusemide is added to 50 parts by weight of deionized water and 50 weights
In the mixed liquor for measuring part ethyl alcohol, 11min 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 75 DEG C of water bath condition after prepolymerization 35min and polymerize 12 hours in 60 DEG C of water bath with thermostatic control, then will
It successively polymerize 5h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively, and 100 parts by weight water are scattered in after product is washed
In, the nitre benzene arsenic heavy stone used as an anchor and 0.01 parts by weight azodiisobutyronitrile (ABIN) of 0.05 parts by weight is added, stirring 1h is placed on 85 DEG C
Then prepolymerization 48min under water bath condition polymerize 28 hours, then by it successively at 80 DEG C, 90 in 40 DEG C of water bath with thermostatic control
DEG C, three-dimensional netted galapectite hydrogel is made after polymerizeing 2h in 100 DEG C of water bath with thermostatic control respectively, place the product in CO2It is overcritical
In high-pressure extraction device, with CO2Supercritical drying 2h is carried out under temperature 50 C and air pressure 20MPa for medium, and three-dimensional can be obtained
Netted galapectite aerogel material.
Embodiment 8
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 2 parts by weight (number
Average molecular weight 1500, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 4.5%),
0.5 parts by weight aoxidize dibenzoyl (BPO), and 10 parts by weight frusemides are added to 50 parts by weight of deionized water and 50 parts by weight of ethanol
Mixed liquor in, stir 60min, be added in galapectite dispersion liquid, ultrasonic disperse 30min, after above-mentioned mixed liquor is vacuumized
1h is kept, normal pressure is then restored to, after repeating vacuum step three times, product is washed, 100 parts by weight water are then dispersed in
In, it is placed under 60 DEG C of water bath condition after prepolymerization 20min in 19 DEG C of water bath with thermostatic control and polymerize 15 hours, then successively by it
It polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, is scattered in after product is washed in 100 parts by weight water, is added
The nitre benzene arsenic heavy stone used as an anchor of 20 parts by weight and 2 parts by weight oxidation dibenzoyl (BPO), stirring 1h are placed on pre-polymerization under 60 DEG C of water bath condition
20min is closed, then polymerize 27 hours in 70 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C of constant temperature
Three-dimensional netted galapectite hydrogel is made after polymerizeing 2h in water-bath respectively, place the product in CO2In supercritical high-pressure extraction device,
With CO2Supercritical drying 4h is carried out at 120 DEG C of temperature and air pressure 13MPa for medium, and three-dimensional netted galapectite airsetting can be obtained
Glue 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. three-dimensional netted galapectite aerogel material, it is characterised in that: galapectite aerogel material average specific surface area is 600-
608m2g-1, nanoscale and micro-meter scale hole, nanoscale hole average out to are existed simultaneously in galapectite aerogel material
10-12nm, is carried out as steps described below by 20-22 μm of average out to of micro-meter scale hole:
Step 1,0.1-20 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, obtains galapectite dispersion liquid；By 0.1-20 parts by weight of styrene sodium sulfonate, 0.01-2 parts by weight
Poly- divinylsiloxanes, 0.01-0.5 parts by weight initiator, 0.05-10 parts by weight frusemide are added to 50 parts by weight deionizations
In 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 uniform,
Vacuum is kept after vacuumizing, is restored to normal pressure, and after repetition vacuumizes three times, washing 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 disperses step 1 product in 100 parts by weight water, warming-in-water to 50-80 DEG C of initiated polymerization, polymerization is anti-
It is at least 48h between seasonable, obtains step 2 product；
Step 3, will step 2 product washing after be scattered in 100 parts by weight water, be added 0.05-20 parts by weight nitre benzene arsenic heavy stone used as an anchor and
0.01-2 parts by weight initiator, after mixing evenly, warming-in-water to 60-100 DEG C of initiated polymerization, polymerization reaction time is at least
For 36h, three-dimensional netted galapectite hydrogel is made；
Step 4, three-dimensional netted galapectite hydrogel is placed in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature
Supercritical drying at least 1h is carried out under 10-300 DEG C and air pressure 1-20MPa, and three-dimensional netted galapectite aerogel material can be obtained；
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 frusemide entered is also dispersed in halloysite nanotubes hollow structure, galapectite nanometer
Pipe hollow structure provides microcellular structure for three-dimensional netted galapectite aerogel material, by vacuumizing, washing, in step 2
Poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed cross-linked structure inside halloysite nanotubes, by furan
Plug rice is supported in halloysite nanotubes, and step 3 makes the poly- divinyl silicon oxygen being located at outside halloysite nanotubes hollow structure
It polymerize under the action of initiator between vinyl functional group on alkane, so that halloysite nanotubes and poly- divinyl silicon
Tridimensional network is collectively formed in oxygen alkane, and above-mentioned tridimensional network provides mesoporous knot for three-dimensional netted galapectite aerogel material
Structure, while nitre benzene arsenic heavy stone used as an anchor being supported in meso-hole structure.
2. three-dimensional netted galapectite aerogel material according to claim 1, it is characterised in that: in step 1, galapectite
Nanotube is 1-10 parts by weight, is added to ultrasonic disperse 1h in the mixed liquor of deionized water and ethyl alcohol, sodium styrene sulfonate 1-
10 parts by weight, poly- divinylsiloxanes are 0.1-1 parts by weight, and initiator is 0.01-0.1 parts by weight, and frusemide is 0.1-5 weight
Part is measured, is added to after stirring 10-60min in the mixed liquor of deionized water and ethyl alcohol, is added in galapectite dispersion liquid, ultrasound point
30min is dissipated, keeps 1h after above-mentioned mixed liquor is vacuumized.
3. three-dimensional netted galapectite aerogel material according to claim 1, it is characterised in that: in step 2, carrying out
Selection polyase 13 0-60min at 50-80 DEG C, is then cooled at 10-60 DEG C and polymerize 12-24h, then successively exist when polymerization reaction
It polymerize 2-8h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
4. three-dimensional netted galapectite aerogel material according to claim 1, it is characterised in that: in step 3, to above-mentioned
0.1-15 parts by weight nitre benzene arsenic heavy stone used as an anchor is added in dispersion liquid and 0.01-1 parts by weight initiator stirs 1h, initiator selects peroxidating two
Benzoyl (BPO) or azodiisobutyronitrile (ABIN), when carrying out polymerization reaction, selection polymerize 20- at 60-100 DEG C
Then 50min is cooled at 30-70 DEG C and polymerize 20-30h, then successively polymerize 2h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
5. three-dimensional netted galapectite aerogel material according to claim 1, it is characterised in that: in step 4, surpassed
The time of critical drying is 2-4h, preferably 3h.
6. the method for preparing three-dimensional netted galapectite aerogel material as claimed in claim 1 to 5, it is characterised in that:
It carries out as steps described below:
Step 1,0.1-20 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, obtains galapectite dispersion liquid；By 0.1-20 parts by weight of styrene sodium sulfonate, 0.01-2 parts by weight
Poly- divinylsiloxanes, 0.01-0.5 parts by weight initiator, 0.05-10 parts by weight frusemide are added to 50 parts by weight deionizations
In 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 uniform,
Vacuum is kept after vacuumizing, is restored to normal pressure, and after repetition vacuumizes three times, washing 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 disperses step 1 product in 100 parts by weight water, warming-in-water to 50-80 DEG C of initiated polymerization, polymerization is anti-
It is at least 48h between seasonable, obtains step 2 product；
Step 3, will step 2 product washing after be scattered in 100 parts by weight water, be added 0.05-20 parts by weight nitre benzene arsenic heavy stone used as an anchor and
0.01-2 parts by weight initiator, after mixing evenly, warming-in-water to 60-100 DEG C of initiated polymerization, polymerization reaction time is at least
For 36h, three-dimensional netted galapectite hydrogel is made；
Step 4, three-dimensional netted galapectite hydrogel is placed in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature
Supercritical drying at least 1h is carried out under 10-300 DEG C and air pressure 1-20MPa, and three-dimensional netted galapectite aerogel material can be obtained；
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 frusemide entered is also dispersed in halloysite nanotubes hollow structure, galapectite nanometer
Pipe hollow structure provides microcellular structure for three-dimensional netted galapectite aerogel material, by vacuumizing, washing, in step 2
Poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed cross-linked structure inside halloysite nanotubes, by furan
Plug rice is supported in halloysite nanotubes, and step 3 makes the poly- divinyl silicon oxygen being located at outside halloysite nanotubes hollow structure
It polymerize under the action of initiator between vinyl functional group on alkane, so that halloysite nanotubes and poly- divinyl silicon
Tridimensional network is collectively formed in oxygen alkane, and above-mentioned tridimensional network provides mesoporous knot for three-dimensional netted galapectite aerogel material
Structure, while nitre benzene arsenic heavy stone used as an anchor being supported in meso-hole structure.
7. the preparation method of three-dimensional netted galapectite aerogel material according to claim 6, it is characterised in that: in step
In 1, halloysite nanotubes are 1-10 parts by weight, are added to ultrasonic disperse 1h, styrene in the mixed liquor of deionized water and ethyl alcohol
Sodium sulfonate is 1-10 parts by weight, and poly- divinylsiloxanes are 0.1-1 parts by weight, and initiator is 0.01-0.1 parts by weight, furan plug
Rice is 0.1-5 parts by weight, is added to after stirring 10-60min in the mixed liquor of deionized water and ethyl alcohol, and galapectite dispersion is added to
In liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor.
8. the preparation method of three-dimensional netted galapectite aerogel material according to claim 6, it is characterised in that: in step
In 2, then selection polyase 13 0-60min at 50-80 DEG C when carrying out polymerization reaction is cooled at 10-60 DEG C and polymerize 12-
For 24 hours, then successively it polymerize 2-8h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
9. the preparation method of three-dimensional netted galapectite aerogel material according to claim 6, it is characterised in that: in step
In 3,0.1-15 parts by weight nitre benzene arsenic heavy stone used as an anchor is added into above-mentioned dispersion liquid and 0.01-1 parts by weight initiator stirs 1h, initiator choosing
Dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN) are selected, selection is at 60-100 DEG C when carrying out polymerization reaction
It polymerize 20-50min, is then cooled at 30-70 DEG C and polymerize 20-30h, then successively polymerize respectively at 80 DEG C, 90 DEG C and 100 DEG C
2h。
10. the preparation method of three-dimensional netted galapectite aerogel material according to claim 6, it is characterised in that: in step
In rapid 4, the time for carrying out supercritical drying is 2-4h, preferably 3h.
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