CN109692631A - Three-dimensional netted galapectite-montmorillonite Composite aerogel material and preparation method thereof - Google Patents
Three-dimensional netted galapectite-montmorillonite Composite aerogel material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides three-dimensional netted galapectite-montmorillonite Composite aerogel material and preparation method thereof, galapectite dispersion liquid is obtained after galapectite dispersion liquid is polymerize with the mixed solution of frusemide, montmorillonite dispersions are prepared again, it is added after initiator that the reaction was continued after two kinds of dispersion liquids are mixed with nitre benzene arsenic heavy stone used as an anchor thereto, obtains three-dimensional netted galapectite-montmorillonite Composite aerogel material.With gradually increasing for soaking time, the drug nitre benzene arsenic heavy stone used as an anchor being carried in mesoporous takes the lead in discharging, and with further increasing for soaking time, the subsequent release of frusemide drug being carried in micropore realizes primary medication, the effect of multiple dosing.
Description
Technical field
The present invention relates to technical field of nano material, multiple more specifically to a kind of three-dimensional netted galapectite-montmorillonite
Close 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, name, structure, pattern and the curling mechanism of Zhuan Quanchao galapectite
[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 three-dimensional netted galapectite-montmorillonite Composite airsetting
Glue material and preparation method thereof uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilizes gas
The meso-hole structure of gel and the microcellular structure of fiber, load different pharmaceutical respectively, realize the ladder-like classification release of drug.
The purpose of the present invention is achieved by following technical proposals.
Three-dimensional netted galapectite-montmorillonite Composite aerogel material and preparation method thereof carries out as steps described below:
Step 1,0.5-15 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 0.5-15 parts by weight of styrene sodium sulfonate, 0.05-2 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 mixing evenly, ultrasound
After being uniformly dispersed, vacuum is kept after vacuumizing, and is then restored to normal pressure, after repeating vacuum step three times, after product is washed,
It is scattered in 100 parts by weight water, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization reaction time at least 50h, washs
It is dispersed in 100 parts by weight water, obtains the dispersion liquid 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 is purchased from Dow corning company.
Step 2, by after 0.05-15 parts by weight montmorillonite drying, dispersed with the montmorillonite that solvent is configured to 0.05-25wt%
Liquid, montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the dispersion liquid of step 2；
Step 3, by the dispersion liquid of 0.5-15 parts by weight step 1, the dispersion liquid of 0.5-35 parts by weight step 2,0.1-20 weight
It measures the nitre benzene arsenic heavy stone used as an anchor solution that part mass fraction is 0.05-20wt% to mix, is scattered in decentralized medium, 0.01-2 is added thereto
Parts by weight initiator, after mixing evenly, warming-in-water to initiated polymerization at 70-90 DEG C, polymerization reaction time at least 37h
Afterwards, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium at 10-300 DEG C of temperature and air pressure 1-20MPa
Supercritical drying at least 1h is carried out, three-dimensional netted galapectite-montmorillonite Composite aerogel material can be obtained.
In step 1,1-10 parts by weight halloysite nanotubes are added to ultrasonic disperse in the mixed solution of water and ethyl alcohol
1h, by 1-10 parts by weight of styrene sodium sulfonate, the poly- divinylsiloxanes of 0.1-1 parts by weight, 0.01-0.1 parts by weight initiator,
0.1-5 parts by weight frusemide is added in the mixed solution of water and ethyl alcohol, is added to above-mentioned solution angstrom after stirring 10-60min
In the stone dispersion liquid of Lip river, ultrasonic disperse 30min keeps vacuum 1h after vacuumizing, when carrying out polymerization reaction, selection is at 70-80 DEG C
It polymerize 12-24h under water bath condition after prepolymerization 30-60min in 40-60 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C,
90 DEG C, it polymerize 2-8h respectively in 100 DEG C of water bath with thermostatic control.
In step 2, montmorillonite drying condition: 60-180 DEG C of temperature, time 5-20h, after the drying of 0.1-10 parts by weight
Montmorillonite be configured to the montmorillonite dispersions that mass fraction is 0.1-20wt% with solvent, by montmorillonite dispersions at 5-35 DEG C
Under 4-10h, then the ultrasonic treatment 6-15h with 50-300W power stirred with the speed mechanical of 150-400r/min.
In step 3, by the dispersion liquid of 1-10 parts by weight step 1, the dispersion liquid of 1-30 parts by weight step 2 and 0.5-15 weight
It measures the nitre benzene arsenic heavy stone used as an anchor solution that part mass fraction is 0.05-15wt% to mix, is scattered in 10-1000 parts by weight decentralized medium, adds
Enter 0.01-1 parts by weight initiator, stirs 1h, selection prepolymerization under 70-90 DEG C of water bath condition when carrying out polymerization reaction
It polymerize 12-24h after 30-60min in 30-50 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
It polymerize 2-8h in water-bath respectively, freeze-drying condition is -5 DEG C of temperature -- 108 DEG C, 0-60 DEG C of humidity, vacuum degree 10-50000pa,
Time 2-48h, supercritical drying time are 2-4h, preferably 3h.
Initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
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-montmorillonite Composite aerogel material, through vacuumizing,
After washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed inside halloysite nanotubes and are formed crosslinking knot
Frusemide is supported in halloysite nanotubes by structure, and step 3 makes the poly- divinyl being located at outside halloysite nanotubes hollow structure
It polymerize under the action of initiator between vinyl functional group on radical siloxane, so that halloysite nanotubes and poly- diethyl
Tridimensional network is collectively formed in alkenyl siloxane, and the montmorillonite being added in step 2 is successfully configured to network pore structure, above-mentioned
Tridimensional network and montmorillonite are successfully configured to network pore structure and together form three-dimensional network pore structure, above-mentioned three-dimensional
Network pore structure provides meso-hole structure for three-dimensional netted galapectite-montmorillonite Composite aerogel material, while by nitre benzene arsenic heavy stone used as an anchor
It is supported in meso-hole structure.
Using scientific and technological (Beijing) the Co., Ltd 3H-2000PS1 type static volumetric method specific surface area of Bei Shide instrument and aperture
The N of the tester analysis composite material that according to the present invention prepared by the method2Adsorption-desorption curve, such as Fig. 1.It can be with from figure
Find out, the N of the material2Adsorption-desorption curve is the IV class isothermal curve of H1 type hysteresis loop in IUPAC classification, i.e., by mesoporous knot
Structure generates.Illustrate that material itself has the pore structure of meso-scale.There is vertical ascent trend from the distribution of low pressure endpoint, can see
Sample interior is as caused by absorption potential strong inside micropore there are more micropore out.By nitrogen adsorption desorption isotherm data,
The sample specific surface area can reach 602.14m2g-1, which exists simultaneously mesoporous-micropore second level pore structure.It is surveyed 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=-0.935/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.389 [- 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
10.98nm, another kind are 20.45 μm, are measured through multiple groups, and nanoscale hole is average up to 10-12nm, and micro-meter scale hole is flat
Up to 20-22 μm.It can be seen that material exists simultaneously nanoscale and micro-meter scale hole.
Using the Nanosem430 field emission scanning electron microscope of Dutch Philips to the method for the invention system of utilization
The microscopic appearance of standby composite material is observed, as shown in Figure 2.It can be seen from the figure that montmorillonite layer is successfully configured to
Network pore structure, aperture size is in mesoporous scale.It is overlapped to form three-dimensional netted halloysite nanotubes and is uniformly dispersed in cover and take off
In native 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 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 three-dimensional netted galapectite-montmorillonite Composite aerogel material N2Adsorption-desorption curve；
Fig. 2 is three-dimensional netted galapectite-montmorillonite Composite aerogel material electromicroscopic photograph；
Fig. 3 is three-dimensional netted galapectite-montmorillonite Composite aerogel material release product test curve；
Fig. 4 is three-dimensional netted galapectite-montmorillonite Composite aerogel material carrying medicament release profiles.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1
6g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 10g sodium styrene sulfonate, 0.5g poly- divinylsiloxanes (number-average molecular weight 3500, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of mole percent 0.5%), 0.6g dibenzoyl peroxide (BPO),
0.3g frusemide is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 13min, is added to galapectite dispersion liquid
In, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, repeats vacuum step three times
Afterwards, it after product being washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 56min in 50 DEG C of constant temperature
It polymerize 15 hours in water-bath, after it is successively then polymerize 5h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, by product
It after washing, is scattered in 100g water, obtains dispersion liquid A；11h is dried into 10g montmorillonite at 180 DEG C, then is configured to solvent
Mass fraction is the montmorillonite dispersions of 20wt%；Montmorillonite dispersions are stirred at 30 DEG C with the speed mechanical of 165r/min
4h, then with the ultrasonic treatment 14h of 226W power, obtain dispersion liquid B；By 2g dispersion liquid A, 22g dispersion liquid B, 5.5g mass fraction
It mixes, is scattered in 1000g decentralized medium for the nitre benzene arsenic heavy stone used as an anchor solution of 10wt%, 0.01g dibenzoyl peroxide is added
(BPO), stirring 1h is placed on prepolymerization 39min under 88 DEG C of water bath condition, then polymerize 19h in 42 DEG C of water bath with thermostatic control,
It is successively respectively then placed into obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, place the product in CO2It is super to face
In boundary's high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 189 DEG C of temperature and air pressure 1MPa for medium, can be obtained angstrom
The multiple dimensioned load medicine aeroge of Lip river stone/montmorillonite.
Embodiment 2
4g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 1g sodium styrene sulfonate, 0.3g poly- divinylsiloxanes (number-average molecular weight 1500, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of mole percent 2.5%), 1g dibenzoyl peroxide (BPO),
0.5g frusemide is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 24min, is added to galapectite dispersion liquid
In, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, repeats vacuum step three times
Afterwards, it after product being washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 45min in 50 DEG C of constant temperature
It polymerize 24 hours in water-bath, after it is successively then polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, by product
It after washing, is scattered in 100g water, obtains dispersion liquid A；20h is dried into 3.4g montmorillonite at 60 DEG C, then is configured to solvent
Mass fraction is the montmorillonite dispersions of 0.1wt%；Montmorillonite dispersions are stirred at 19 DEG C with the speed mechanical of 293r/min
It mixes 5h, then with the ultrasonic treatment 9h of 300W power, obtains dispersion liquid B；By 1g dispersion liquid A, 12g dispersion liquid B, 8.6g mass fraction
It mixes, is scattered in 10g decentralized medium for the nitre benzene arsenic heavy stone used as an anchor solution of 0.65wt%, is added 0.3g dibenzoyl peroxide (BPO),
Stirring 1h is placed on prepolymerization 60min under 70 DEG C of water bath condition, then polymerize 23h in 30 DEG C of water bath with thermostatic control, then will
It successively respectively places obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, and place the product in CO2Supercritical, high pressure
In extraction equipment, with CO2Supercritical drying 3h is carried out at 55 DEG C of temperature and air pressure 3MPa for medium, and galapectite/illiteracy can be obtained
The de- multiple dimensioned load medicine aeroge of soil.
Embodiment 3
8g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 4g sodium styrene sulfonate, 0.4g poly- divinylsiloxanes (number-average molecular weight 2500, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 3%), 0.44g dibenzoyl peroxide (BPO),
5g frusemide is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 34min, is added in galapectite dispersion liquid,
Ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, after repeating vacuum step three times,
It after product is washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 60min in 50 DEG C of water bath with thermostatic control
Middle polymerization 20 hours, after it is successively then polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, product is washed
Afterwards, it is scattered in 100g water, obtains dispersion liquid A；5h is dried into 2.6g montmorillonite at 95 DEG C, then is configured to quality point with solvent
Number is the montmorillonite dispersions of 8wt%；Montmorillonite dispersions are stirred into 8h at 25 DEG C with the speed mechanical of 400r/min, then are used
The ultrasonic treatment 6h of 120W power, obtains dispersion liquid B；It is 0.05wt% by 6g dispersion liquid A, 3g dispersion liquid B, 0.5g mass fraction
Nitre benzene arsenic heavy stone used as an anchor solution mixing, be scattered in 562g decentralized medium, be added 0.9g dibenzoyl peroxide (BPO), stir 1h after
It is placed in prepolymerization 55min under 71 DEG C of water bath condition, 90h is then polymerize in 32 DEG C of water bath with thermostatic control, then it successively exists
80 DEG C, obtained solution after 2h is respectively placed in 100 DEG C of water bath with thermostatic control, place the product in CO by 90 DEG C2Supercritical high-pressure extraction device
In, with CO2Supercritical drying 3h is carried out at 16 DEG C of temperature and air pressure 15MPa for medium, and the more rulers of galapectite/montmorillonite can be obtained
Degree carries medicine aeroge.
Embodiment 4
9g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 6g sodium styrene sulfonate, 0.1g poly- divinylsiloxanes (number-average molecular weight 1000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 4%), 0.01g dibenzoyl peroxide (BPO),
0.22g frusemide is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 60min, is added to galapectite dispersion liquid
In, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, repeats vacuum step three times
Afterwards, it after product being washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 55min in 50 DEG C of constant temperature
It polymerize 12 hours in water-bath, after it is successively then polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, by product
It after washing, is scattered in 100g water, obtains dispersion liquid A；6h is dried into 0.1g montmorillonite at 144 DEG C, then is configured to solvent
Mass fraction is the montmorillonite dispersions of 4.6wt%；Montmorillonite dispersions are stirred at 5 DEG C with the speed mechanical of 256r/min
10h, then with the ultrasonic treatment 15h of 260W power, obtain dispersion liquid B；By 5.3g dispersion liquid A, 1g dispersion liquid B, 0.89g mass point
The nitre benzene arsenic heavy stone used as an anchor solution that number is 15wt% mixes, and is scattered in 352g decentralized medium, and 0.06g dibenzoyl peroxide is added
(BPO), stirring 1h is placed on prepolymerization 53min under 90 DEG C of water bath condition, then polymerize 16h in 50 DEG C of water bath with thermostatic control,
It is successively respectively then placed into obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, place the product in CO2It is super to face
In boundary's high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 300 DEG C of temperature and air pressure 20MPa for medium, can be obtained angstrom
The multiple dimensioned load medicine aeroge of Lip river stone/montmorillonite.
Embodiment 5
1g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 5g sodium styrene sulfonate, 0.7g poly- divinylsiloxanes (number-average molecular weight 4000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 1%), 0.7g azodiisobutyronitrile (ABIN),
0.1g frusemide is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 29min, is added to galapectite dispersion liquid
In, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, repeats vacuum step three times
Afterwards, it after product being washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 31min in 50 DEG C of constant temperature
It polymerize 13 hours in water-bath, after it is successively then polymerize 4h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, by product
It after washing, is scattered in 100g water, obtains dispersion liquid A；18h is dried into 6.5g montmorillonite at 120 DEG C, then is configured to solvent
Mass fraction is the montmorillonite dispersions of 18wt%；Montmorillonite dispersions are stirred at 35 DEG C with the speed mechanical of 332r/min
3h, then with the ultrasonic treatment 8h of 250W power, obtain dispersion liquid B；It is by 10g dispersion liquid A, 9g dispersion liquid B, 15g mass fraction
The nitre benzene arsenic heavy stone used as an anchor solution of 5.2wt% mixes, and is scattered in 152g decentralized medium, is added 1g azodiisobutyronitrile (ABIN), stirring
1h is placed on prepolymerization 30min under 76 DEG C of water bath condition, and 15h is then polymerize in 48 DEG C of water bath with thermostatic control, then by its according to
Secondary respectively to place obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, place the product in CO2Supercritical, high pressure extraction
In device, with CO2Supercritical drying 3h is carried out at 225 DEG C of temperature and air pressure 4MPa for medium, and galapectite/montmorillonite can be obtained
Multiple dimensioned load medicine aeroge.
Embodiment 6
10g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 8g sodium styrene sulfonate, (number-average molecular weight 3000, contents of ethylene rubs the poly- divinylsiloxanes of 1g
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of your percentage 1.5%), 0.5g azodiisobutyronitrile (ABIN),
3.5g frusemide is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 10min, is added to galapectite dispersion liquid
In, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, repeats vacuum step three times
Afterwards, it after product being washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 30min in 50 DEG C of constant temperature
It polymerize in water-bath 21 hours, after it is successively then distinguished polyase 13 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, by product
It after washing, is scattered in 100g water, obtains dispersion liquid A；15h is dried into 3g montmorillonite at 66 DEG C, then is configured to matter with solvent
Measure the montmorillonite dispersions that score is 0.5wt%；Montmorillonite dispersions are stirred at 6 DEG C with the speed mechanical of 150r/min
9h, then with the ultrasonic treatment 12h of 50W power, obtain dispersion liquid B；It is by 9g dispersion liquid A, 30g dispersion liquid B, 2.6g mass fraction
The nitre benzene arsenic heavy stone used as an anchor solution of 13wt% mixes, and is scattered in 998g decentralized medium, is added 0.65g azodiisobutyronitrile (ABIN), stirs
It mixes 1h and is placed on prepolymerization 44min under 85 DEG C of water bath condition, 28h is then polymerize in 35 DEG C of water bath with thermostatic control, then by it
Obtained solution after 2h is respectively successively placed in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, place the product in CO2Supercritical, high pressure extraction
It takes in device, with CO2Supercritical drying 3h is carried out at 10 DEG C of temperature and air pressure 10MPa for medium, and it is de- that galapectite/illiteracy can be obtained
The multiple dimensioned load medicine aeroge of soil.
Embodiment 7
15g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 15g sodium styrene sulfonate, (number-average molecular weight 500, contents of ethylene rubs the poly- divinylsiloxanes of 2g
The poly dimethyl divinylsiloxanes of the amino list sealing end of your percentage 5%), 0.5g azodiisobutyronitrile (ABIN), 10g furan
Plug rice is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 24min, is added in galapectite dispersion liquid, ultrasound
Disperse 30min, 1h is kept after above-mentioned mixed liquor is vacuumized, be then restored to normal pressure, after repeating vacuum step three times, will produce
It after object washing, is scattered in 100g water, is placed under 70 DEG C of water bath condition after prepolymerization 45min and gathers in 40 DEG C of water bath with thermostatic control
It closes 24 hours, after it is successively then polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, after product is washed,
It is scattered in 100g water, obtains dispersion liquid A；20h is dried into 15g montmorillonite at 60 DEG C, then is configured to mass fraction with solvent
For the montmorillonite dispersions of 25wt%；Montmorillonite dispersions are stirred into 5h at 19 DEG C with the speed mechanical of 293r/min, then are used
The ultrasonic treatment 9h of 300W power, obtains dispersion liquid B；It is 20wt% by 15g dispersion liquid A, 35g dispersion liquid B, 20g mass fraction
Nitre benzene arsenic heavy stone used as an anchor solution mixing, be scattered in 10g decentralized medium, be added 2g azodiisobutyronitrile (ABIN), stirring 1h be placed on
Prepolymerization 60min under 70 DEG C of water bath condition, then polymerize 23h in 30 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C,
90 DEG C, obtained solution after 2h is respectively placed in 100 DEG C of water bath with thermostatic control, place the product in CO2In supercritical high-pressure extraction device, with
CO2Supercritical drying 4h is carried out at 20 DEG C of temperature and air pressure 6MPa for medium, and the multiple dimensioned load medicine of galapectite/montmorillonite can be obtained
Aeroge.
Embodiment 8
0.5g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
To galapectite dispersion liquid, by 0.5g sodium styrene sulfonate, 0.05g poly- divinylsiloxanes (number-average molecular weight 5000, vinyl
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of content mole percent 0.1%), 0.01g azodiisobutyronitrile
(ABIN), 0.05g frusemide is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 29min, is added to galapectite
In dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, and repetition vacuumizes step
Suddenly three times after, after product is washed, be scattered in 100g water, be placed under 80 DEG C of water bath condition after prepolymerization 31min at 60 DEG C
Water bath with thermostatic control in polymerize 13 hours, after it is successively then polymerize 4h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control,
It after product is washed, is scattered in 100g water, obtains dispersion liquid A；By 0.05g montmorillonite at 120 DEG C dry 18h, then with molten
Agent is configured to the montmorillonite dispersions that mass fraction is 0.05wt%；By montmorillonite dispersions with the speed of 332r/min at 35 DEG C
Mechanical stirring 3h is spent, then with the ultrasonic treatment 8h of 250W power, obtains dispersion liquid B；By 0.5g dispersion liquid A, 0.5g dispersion liquid B,
The nitre benzene arsenic heavy stone used as an anchor solution that 0.1g mass fraction is 0.05wt% mixes, and is scattered in 152g decentralized medium, and 0.01g azo two is added
Isobutyronitrile (ABIN), stirring 1h are placed on prepolymerization 30min under 76 DEG C of water bath condition, then gather in 48 DEG C of water bath with thermostatic control
15h is closed, it is successively respectively then placed into obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, place the product in
CO2In supercritical high-pressure extraction device, with CO2Supercritical drying 2h is carried out at 275 DEG C of temperature and air pressure 18MPa for medium, it can
Obtain the multiple dimensioned load medicine aeroge of galapectite/montmorillonite.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. three-dimensional netted galapectite-montmorillonite Composite aerogel material, it is characterised in that: galapectite-montmorillonite Composite aeroge
Material average specific surface area is 600-608m2g-1, exist simultaneously in galapectite-montmorillonite Composite aerogel material nanoscale and
Micro-meter scale hole, nanoscale hole average out to 10-12nm, 20-22 μm of average out to of micro-meter scale hole, as steps described below
It carries out:
Step 1,0.5-15 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 0.5-15 parts by weight of styrene sodium sulfonate, 0.05-2 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 mixing evenly, ultrasonic disperse
After uniformly, vacuum is kept after vacuumizing, and is then restored to normal pressure, after repeating vacuum step three times, after product is washed, dispersion
In 100 parts by weight water, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization reaction time at least 50h, washing dispersion
Into 100 parts by weight water, the dispersion liquid of step 1 is obtained；
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, by after 0.05-15 parts by weight montmorillonite drying, the montmorillonite dispersions of 0.05-25wt% are configured to solvent,
Montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the dispersion liquid of step 2；
Step 3, by the dispersion liquid of 0.5-15 parts by weight step 1, the dispersion liquid of 0.5-35 parts by weight step 2,0.1-20 parts by weight
The nitre benzene arsenic heavy stone used as an anchor solution that mass fraction is 0.05-20wt% mixes, and is scattered in decentralized medium, and 0.01-2 weight is added thereto
Part initiator, after mixing evenly, warming-in-water to initiated polymerization at 70-90 DEG C will after polymerization reaction time at least 37h
Product is placed in CO2In supercritical high-pressure extraction device, with CO2Surpassed at 10-300 DEG C of temperature and air pressure 1-20MPa for medium
Three-dimensional netted galapectite-montmorillonite Composite aerogel material can be obtained in critical drying at least 1h.
2. three-dimensional netted galapectite-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step
In rapid 1,1-10 parts by weight halloysite nanotubes are added to ultrasonic disperse 1h in the mixed solution of water and ethyl alcohol, by 1-10 weight
Part sodium styrene sulfonate, the poly- divinylsiloxanes of 0.1-1 parts by weight, 0.01-0.1 parts by weight initiator, 0.1-5 parts by weight furan
Plug rice is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added in galapectite dispersion liquid after stirring 10-60min,
Ultrasonic disperse 30min keeps vacuum 1h after vacuumizing, when carrying out polymerization reaction, selection is pre- under 70-80 DEG C of water bath condition
It polymerize 12-24h after polyase 13 0-60min in 40-60 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C
It polymerize 2-8h in water bath with thermostatic control respectively.
3. three-dimensional netted galapectite-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step
In rapid 2, montmorillonite drying condition: 60-180 DEG C of temperature, time 5-20h, by montmorillonite of the 0.1-10 parts by weight after dry with molten
Agent is configured to the montmorillonite dispersions that mass fraction is 0.1-20wt%, by montmorillonite dispersions with 150- at 5-35 DEG C
The speed mechanical of 400r/min stirs 4-10h, then the ultrasonic treatment 6-15h with 50-300W power.
4. three-dimensional netted galapectite-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step
In rapid 3, by the dispersion liquid of 1-10 parts by weight step 1, the dispersion liquid of 1-30 parts by weight step 2 and 0.5-15 parts by weight mass fraction
It mixes, is scattered in 10-1000 parts by weight decentralized medium for the nitre benzene arsenic heavy stone used as an anchor solution of 0.05-15wt%, 0.01-1 weight is added
Part initiator stirs 1h, when carrying out polymerization reaction selection under 70-90 DEG C of water bath condition after prepolymerization 30-60min
It polymerize 12-24h in 30-50 DEG C of water bath with thermostatic control, then successively gathers it respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
2-8h is closed, freeze-drying condition is -5 DEG C of temperature -- 108 DEG C, 0-60 DEG C of humidity, vacuum degree 10-50000pa, time 2-48h, surpass
Critical drying time is 2-4h, preferably 3h.
5. three-dimensional netted galapectite-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: cause
Agent selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
6. three-dimensional netted galapectite-montmorillonite Composite aerogel material preparation method, it is characterised in that: as steps described below into
Row:
Step 1,0.5-15 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 0.5-15 parts by weight of styrene sodium sulfonate, 0.05-2 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 mixing evenly, ultrasonic disperse
After uniformly, vacuum is kept after vacuumizing, and is then restored to normal pressure, after repeating vacuum step three times, after product is washed, dispersion
In 100 parts by weight water, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization reaction time at least 50h, washing dispersion
Into 100 parts by weight water, the dispersion liquid of step 1 is obtained；
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, by after 0.05-15 parts by weight montmorillonite drying, the montmorillonite dispersions of 0.05-25wt% are configured to solvent,
Montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the dispersion liquid of step 2；
Step 3, by the dispersion liquid of 0.5-15 parts by weight step 1, the dispersion liquid of 0.5-35 parts by weight step 2,0.1-20 parts by weight
The nitre benzene arsenic heavy stone used as an anchor solution that mass fraction is 0.05-20wt% mixes, and is scattered in decentralized medium, and 0.01-2 weight is added thereto
Part initiator, after mixing evenly, warming-in-water to initiated polymerization at 70-90 DEG C will after polymerization reaction time at least 37h
Product is placed in CO2In supercritical high-pressure extraction device, with CO2Surpassed at 10-300 DEG C of temperature and air pressure 1-20MPa for medium
Three-dimensional netted galapectite-montmorillonite Composite aerogel material can be obtained in critical drying at least 1h；
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-montmorillonite Composite aerogel material, by vacuumizing, washing
Afterwards, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, 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 the montmorillonite being added in step 2 is successfully configured to network pore structure, above-mentioned three-dimensional
Reticular structure and montmorillonite are successfully configured to network pore structure and together form three-dimensional network pore structure, above-mentioned three-dimensional network
Pore structure provides meso-hole structure for three-dimensional netted galapectite-montmorillonite Composite aerogel material, while nitre benzene arsenic heavy stone used as an anchor being loaded
In meso-hole structure.
7. the preparation method of three-dimensional netted galapectite-montmorillonite Composite aerogel material according to claim 6, feature
It is: in step 1,1-10 parts by weight halloysite nanotubes is added to ultrasonic disperse 1h in the mixed solution of water and ethyl alcohol,
By 1-10 parts by weight of styrene sodium sulfonate, the poly- divinylsiloxanes of 0.1-1 parts by weight, 0.01-0.1 parts by weight initiator,
0.1-5 parts by weight frusemide is added in the mixed solution of water and ethyl alcohol, is added to above-mentioned solution angstrom after stirring 10-60min
In the stone dispersion liquid of Lip river, ultrasonic disperse 30min keeps vacuum 1h after vacuumizing, when carrying out polymerization reaction, selection is at 70-80 DEG C
It polymerize 12-24h under water bath condition after prepolymerization 30-60min in 40-60 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C,
90 DEG C, it polymerize 2-8h respectively in 100 DEG C of water bath with thermostatic control.
8. the preparation method of three-dimensional netted galapectite-montmorillonite Composite aerogel material according to claim 6, feature
It is: in step 2, montmorillonite drying condition: 60-180 DEG C of temperature, time 5-20h, by illiteracy of the 0.1-10 parts by weight after dry
De- soil is configured to the montmorillonite dispersions that mass fraction is 0.1-20wt% with solvent, by montmorillonite dispersions at 5-35 DEG C with
The speed mechanical of 150-400r/min stirs 4-10h, then the ultrasonic treatment 6-15h with 50-300W power.
9. the preparation method of three-dimensional netted galapectite-montmorillonite Composite aerogel material according to claim 6, feature
It is: in step 3, by the dispersion liquid of 1-10 parts by weight step 1, the dispersion liquid of 1-30 parts by weight step 2 and 0.5-15 weight
The nitre benzene arsenic heavy stone used as an anchor solution that part mass fraction is 0.05-15wt% mixes, and is scattered in 10-1000 parts by weight decentralized medium, is added
0.01-1 parts by weight initiator stirs 1h, selection prepolymerization 30- under 70-90 DEG C of water bath condition when carrying out polymerization reaction
It polymerize 12-24h after 60min in 30-50 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C of thermostatted water
It polymerize 2-8h in bath respectively, freeze-drying condition is -5 DEG C of temperature -- 108 DEG C, 0-60 DEG C of humidity, vacuum degree 10-50000pa, when
Between 2-48h, the supercritical drying time be 2-4h, preferably 3h.
10. the preparation method of three-dimensional netted galapectite-montmorillonite Composite aerogel material according to claim 6, special
Sign is: initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
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| CN113501683A (en) * | 2021-07-13 | 2021-10-15 | 浙江理工大学 | Preparation method of boehmite-nano cellulose fiber-halloysite composite flame-retardant material |
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| CN105565774A (en) * | 2015-05-11 | 2016-05-11 | 天津城建大学 | High-strength high-thermal-insulation silica aerogel and preparation method thereof |
| CN106316329A (en) * | 2015-06-17 | 2017-01-11 | 天津城建大学 | Inorganic foamed building heat insulation board and making method thereof |
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2017
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| US20030232727A1 (en) * | 2002-04-22 | 2003-12-18 | Hoy Edgar Franklin | additives for preparing rheology-modified aqueous fluids |
| CN103520113A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院兰州化学物理研究所 | Halloysite nano composite gel microspheres and preparation method thereof |
| CN103599734A (en) * | 2013-11-22 | 2014-02-26 | 中国工程物理研究院核物理与化学研究所 | Aerogel material and preparation method thereof |
| CN105565774A (en) * | 2015-05-11 | 2016-05-11 | 天津城建大学 | High-strength high-thermal-insulation silica aerogel and preparation method thereof |
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| CN113501683A (en) * | 2021-07-13 | 2021-10-15 | 浙江理工大学 | Preparation method of boehmite-nano cellulose fiber-halloysite composite flame-retardant material |
| CN113501683B (en) * | 2021-07-13 | 2022-06-21 | 浙江理工大学 | Preparation method of boehmite-nano cellulose fiber-halloysite composite flame-retardant material |
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