CN109692152A - Graphene-galapectite aerogel composite and preparation method thereof - Google Patents
Graphene-galapectite aerogel composite and preparation method thereof Download PDFInfo
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Abstract
The present invention provides graphene-galapectite aerogel composite and preparation method thereof, galapectite dispersion liquid is obtained after galapectite dispersion liquid is polymerize with the mixed solution of dexamethasone, then prepare dense H2SO, graphite powder and KMnO4Dispersion liquid, will above two dispersion liquid mix after be added after initiator and Lovastatin that the reaction was continued thereto, obtain graphene-galapectite aerogel composite.With gradually increasing for soaking time, the drug Lovastatin being carried in mesoporous takes the lead in discharging, and with further increasing for soaking time, the subsequent release of dexamethasone drug being carried in micropore realizes primary medication, the effect of multiple dosing.
Description
Technical field
The present invention relates to technical field of nano material, more specifically to a kind of graphene-galapectite composite 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 deficiency in the prior art, provide a kind of graphene-galapectite aerogel composite and
Preparation method uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilizes Jie of aeroge
The microcellular structure of pore 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.
Graphene-galapectite aerogel composite 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 dexamethasone is added to 50 parts by weight
In the mixed liquor of deionized water and 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, is surpassed
Sound is uniformly dispersed, and 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, for warming-in-water to 70-80 DEG C of initiated polymerization, polymerization time is 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 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 the dense H of 0.5-10 parts by weight2SO4It is mixed with 0.1-15 parts by weight of graphite powder, 0.5-15 parts by weight is added
KMnO4, said mixture is placed in ice-water bath after being stirred to react at least 12h, 50-250 parts by weight water, stirring is added thereto
After uniformly, 350-550 parts by weight water and 8-55 parts by weight H are added in Xiang Shangshu solution2O2, stir evenly, product is washed to close
After neutrality, 100 parts by weight water are added into product, ultrasonic disperse is uniform, obtains the dispersion liquid of step 2；
Step 3, after the dispersion liquid of step 1 and step 2 being mixed, 0.01-2 parts by weight initiator, 0.01- are added thereto
10 parts by weight Lovastatins, after mixing evenly, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization time are at least 60h
Afterwards, it is added in Xiang Shangshu reaction solution after 0.5-15 parts by weight ascorbic acid after the reaction was continued 10-40h, place the product in CO2It is super to face
In boundary's high-pressure extraction device, with CO2Supercritical drying at least 1h is carried out at 30-60 DEG C of temperature and air pressure 5-15MPa for medium,
Graphene-galapectite aerogel composite 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 dexamethasone is added in the mixed solution of water and ethyl alcohol, is added to above-mentioned solution after stirring 10-60min
In galapectite dispersion liquid, ultrasonic disperse 30min keeps vacuum 1h after vacuumizing.
In step 1, when carrying out polymerization reaction selection under 70-80 DEG C of water bath condition after prepolymerization 30-60min
It polymerize 12-24h in 40-60 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
Close 2-8h.
In step 2, by the dense H of 1-5 parts by weight2SO4It is mixed with 0.5-10 parts by weight of graphite powder, 1-10 parts by weight is added
KMnO4, said mixture is placed in ice-water bath and is stirred, maintenance system temperature is 1-3 DEG C in whipping process, sustained response 1-
After 10h, 100-200 parts by weight water is added, stirs 1-4h, after being cooled to room temperature, 400-500 parts by weight are added in Xiang Shangshu solution
Water and 10-50 parts by weight H2O2, stir 1-6h.
In step 3, the addition 0.01-1 parts by weight initiator into mixed dispersion liquid, 0.05-5 parts by weight Lovastatin,
Stirring 1-10h is placed under 70-80 DEG C of water bath condition after prepolymerization 30-60min, is being polymerize in 40-60 DEG C of water bath with thermostatic control
12-24h is placed in 80-200 DEG C of water after it is successively then polymerize 2-8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After reacting 1-10h in hot kettle, 1-10 parts by weight ascorbic acid is added thereto, reaction temperature is controlled at 20-100 DEG C, overcritical
Drying condition is dry 2-4h, preferably 3h under 33-55 DEG C of temperature and air pressure 7-10MPa.
Initiator uses 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 dexamethasone of middle addition are also dispersed in halloysite nanotubes hollow structure, Ai Luo
Stone nanotube hollow structure provides microcellular structure for graphene-galapectite aerogel composite, by vacuumizing, washing
Afterwards, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed cross-linked structure inside halloysite nanotubes, will
Dexamethasone is supported in halloysite nanotubes, 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 siloxanes, so that halloysite nanotubes and poly- divinyl
Tridimensional network is collectively formed in radical siloxane, the dense H being added in step 22SO4, graphite powder and KMnO4It reacts to form stone
Black alkene, graphene sheet layer are successfully configured to network pore structure, and above-mentioned tridimensional network and graphene sheet layer are built-up
Network pore structure together forms three-dimensional network pore structure, and above-mentioned three-dimensional network pore structure is that graphene-galapectite is multiple
It closes aerogel material and meso-hole structure is provided, while Lovastatin being supported in meso-hole structure.
Using scientific and technological (Beijing) the Co., Ltd 3H-2000PS1 type static volumetric method specific surface area of Bei Shide instrument and aperture
The N of the tester analysis composite material that according to the present invention prepared by the method2Adsorption-desorption curve, such as Fig. 1.It can be with from figure
Find out, the N2 adsorption-desorption curve of the material is the IV class isothermal curve of H1 type hysteresis loop in IUPAC classification, i.e., by mesoporous knot
Structure generates.Illustrate that material itself has the pore structure of meso-scale.There is vertical ascent trend from the distribution of low pressure endpoint, can see
Sample interior is as caused by absorption potential strong inside micropore there are more micropore out.By nitrogen adsorption desorption isotherm data,
The sample specific surface area can reach 602.14m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, surveys through multiple groups
The average specific surface area for measuring material is 600-608m2g-1。
By N2Data in adsorption-desorption curve are substituted into correlation values, can be arranged by BJH formula and Kelvin equation
Obtain the accounting equation r in aperturek=-0.952/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.353 [- 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
10.34nm, another kind are 20.53 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 graphene sheet 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 graphite
In alkene three-dimensional network hole, the building of dual load system is realized.
Reference literature (Li Degui, the preparation and characterization of nano-cellulose base Thermosensitive Material Used for Controlled Releasing of Medicine, South China Science & Engineering University,
2016) method described in carries out sustained release performance test characterization to material prepared by the present invention.Two sustained release steps are delayed respectively
It releases product and carries out infrared spectroscopy detection, as a result as shown in figure 3, by being compareed with standard diagram, it was demonstrated that take the lead in release is that Lip river is cut down
Statin, what is then discharged is dexamethasone, realizes the multiple dimensioned load and repeatedly release of different pharmaceutical.
The composite material carrying medicament prepared using the method for the invention is placed in simulation human consumption's liquid, measurement
Its drug release effect, figure 4, it is seen that gradually increasing with soaking time, the drug Lip river being carried in mesoporous is cut down
Statin takes the lead in discharging, and with further increasing for soaking time, the subsequent release of dexamethasone drug being carried in micropore is realized
Primary medication, the effect of multiple dosing.
Detailed description of the invention
Fig. 1 is graphene-galapectite aerogel composite N2Adsorption-desorption curve；
Fig. 2 is graphene-galapectite aerogel composite electromicroscopic photograph；
Fig. 3 is graphene-galapectite aerogel composite release product test curve；
Fig. 4 is graphene-galapectite aerogel composite carrying medicament release profiles.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1
Step 1,1g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 2g sodium styrene sulfonate, 0.1g poly- divinylsiloxanes (number-average molecular weight 5000, ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of base content mole percent 5%), 0.02g dibenzoyl peroxide
(BPO), 0.1g dexamethasone is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 20min, 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 75 DEG C of water bath condition after prepolymerization 30min at 50 DEG C
Water bath with thermostatic control in polymerize 15 hours, after it is successively then polymerize 5h 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 galapectite and carry medicine dispersion liquid；
Step 2, by the dense H of 1g2SO4It is mixed with 0.5g graphite powder, 4gKMnO is added4, said mixture is placed in ice-water bath
Stirring, maintenance system temperature is no more than 2 DEG C, sustained response 1h in whipping process, and 120g water is added, and stirs 1h, is cooled to room
450g water and 12gH is added in temperature2O2, 1h is stirred, obtained product is washed with water into removing metal ion, then washed with decentralized medium
It washs to close to after neutrality, 100g water, ultrasonic disperse 2h is added；
Step 3, the product of step 1 and step 2 is mixed, is added 0.5g dibenzoyl peroxide (BPO), 0.05g is cut down Lip river
Statin, stirring 2h is placed under 75 DEG C of water bath condition after prepolymerization 30min to be polymerize 15 hours in 50 DEG C of water bath with thermostatic control, with
After it is successively polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control afterwards, 1h is reacted in 100 DEG C of water heating kettles, is added
Enter 2g ascorbic acid, temperature is controlled at 60 DEG C, and reaction time 10h, place the product in CO2In supercritical high-pressure extraction device,
With CO2Supercritical drying 3h is carried out at 35 DEG C of temperature and air pressure 7MPa for medium, and it is multiple dimensioned that graphene/galapectite can be obtained
Carry medicine aeroge.
Embodiment 2
Step 1,10g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 4g sodium styrene sulfonate, 0.2g poly- divinylsiloxanes (number-average molecular weight 5000, ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of base content mole percent 0.1%), 0.01g azodiisobutyronitrile
(ABIN), 1g dexamethasone is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 10min, 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 75 DEG C of water bath condition after prepolymerization 35min at 50 DEG C
Water bath with thermostatic control in polymerize 12 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,
It after product is washed, is scattered in 100g water, obtains galapectite and carry medicine dispersion liquid；
Step 2, by the dense H of 2g2SO4It is mixed with 3g graphite powder, 6gKMnO is added4, said mixture is placed in ice-water bath and is stirred
It mixes, maintenance system temperature is no more than 2 DEG C, sustained response 4h in whipping process, and 100g water is added, and 2h is stirred, is cooled to room temperature,
400g water and 10gH is added2O2, stir 2h, obtained product washed with water into removing metal ion, then with decentralized medium wash to
Close to after neutral, 100g water, ultrasonic disperse 4h is added；
Step 3, the product of step 1 and step 2 is mixed, is added 0.01g azodiisobutyronitrile (ABIN), 1g cuts down him in Lip river
Spit of fland, stirring 5h is placed under 75 DEG C of water bath condition after prepolymerization 40min polymerize 12 hours in 50 DEG C of water bath with thermostatic control, then
After it is successively distinguished polyase 13 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 4h is reacted in 80 DEG C of water heating kettles, and 6g is added
Ascorbic acid, temperature are controlled at 20 DEG C, and reaction time 20h, place the product in CO2In supercritical high-pressure extraction device, with CO2
Supercritical drying 3h is carried out at 33 DEG C of temperature and air pressure 8MPa for medium, and the multiple dimensioned load medicine of graphene/galapectite can be obtained
Aeroge.
Embodiment 3
Step 1,3g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 1g sodium styrene sulfonate, 0.3g poly- divinylsiloxanes (number-average molecular weight 1000, ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of base content mole percent 4%), 0.05g azodiisobutyronitrile
(ABIN), 1.5g dexamethasone is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 30min, is added to Ai Luo
In stone dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, and repetition vacuumizes
Step three times after, after product is washed, be scattered in 100g water, be placed under 75 DEG C of water bath condition after prepolymerization 40min 50
DEG C water bath with thermostatic control in polymerize 18 hours, it is successively then polymerize 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively
Afterwards, it after product being washed, is scattered in 100g water, obtains galapectite and carry medicine dispersion liquid；
Step 2, by the dense H of 3g2SO4It is mixed with 10g graphite powder, 8gKMnO is added4, said mixture is placed in ice-water bath
Stirring, maintenance system temperature is no more than 2 DEG C, sustained response 6h in whipping process, and 140g water is added, and stirs 4h, is cooled to room
440g water and 50gH is added in temperature2O2, 3h is stirred, obtained product is washed with water into removing metal ion, then washed with decentralized medium
It washs to close to after neutrality, 100g water, ultrasonic disperse 2.5h is added；
Step 3, the product of step 1 and step 2 is mixed, is added 0.6g azodiisobutyronitrile (ABIN), 3g Lovastatin,
Stirring 1h is placed under 75 DEG C of water bath condition after prepolymerization 60min to be polymerize 18 hours in 50 DEG C of water bath with thermostatic control, then will
After it successively polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 10h is reacted in 120 DEG C of water heating kettles, and 1g is added
Ascorbic acid, temperature are controlled at 100 DEG C, and reaction time 25h, place the product in CO2In supercritical high-pressure extraction device, with CO2
Supercritical drying 3h is carried out at 40 DEG C of temperature and air pressure 8.5MPa for medium, and the multiple dimensioned load of graphene/galapectite can be obtained
Medicine aeroge.
Embodiment 4
Step 1,5g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 6g sodium styrene sulfonate, 0.8g poly- divinylsiloxanes (number-average molecular weight 3000, ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of base content mole percent 2%), 0.08g dibenzoyl peroxide
(BPO), 5g dexamethasone is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 50min, is added to galapectite point
In dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats vacuum step
It after three times, after product is washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 60min at 50 DEG C
It polymerize 20 hours in water bath with thermostatic control, it, will after it is successively then polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
It after product washing, is scattered in 100g water, obtains galapectite and carry medicine dispersion liquid；
Step 2, by the dense H of 4g2SO4It is mixed with 6g graphite powder, 10gKMnO is added4, said mixture is placed in ice-water bath
Stirring, maintenance system temperature is no more than 2 DEG C, sustained response 8h in whipping process, and 200g water is added, and stirs 2.5h, is cooled to
500g water and 30gH is added in room temperature2O2, 4h is stirred, obtained product is washed with water into removing metal ion, then use decentralized medium
100g water, ultrasonic disperse 3h is added to close to after neutrality in washing；
Step 3, the product of step 1 and step 2 is mixed, is added 0.7g dibenzoyl peroxide (BPO), 5g cuts down him in Lip river
Spit of fland, stirring 6h is placed under 75 DEG C of water bath condition after prepolymerization 45min polymerize 20 hours in 50 DEG C of water bath with thermostatic control, then
After it is successively polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 6h is reacted in 160 DEG C of water heating kettles, is added
8g ascorbic acid, temperature are controlled at 80 DEG C, and reaction time 35h, place the product in CO2In supercritical high-pressure extraction device, with
CO2Supercritical drying 3h is carried out under temperature 50 C and air pressure 9MPa for medium, and the multiple dimensioned load of graphene/galapectite can be obtained
Medicine aeroge.
Embodiment 5
Step 1,8g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 10g sodium styrene sulfonate, 0.6g poly- divinylsiloxanes (number-average molecular weight 4000, second
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of amount vinyl content mole percent 1.5%), 0.1g diphenyl peroxide first
Acyl (BPO), 3g dexamethasone are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, are stirred 40min, are 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 75 DEG C of water bath condition after prepolymerization 50min at 50 DEG C
Water bath with thermostatic control in polymerize 24 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 galapectite and carry medicine dispersion liquid；
Step 2, by the dense H of 4.5g2SO4It is mixed with 8g graphite powder, 1gKMnO is added4, said mixture is placed in ice-water bath
Stirring, maintenance system temperature is no more than 2 DEG C, sustained response 7h in whipping process, and 160g water is added, and stirs 3h, is cooled to room
460g water and 20gH is added in temperature2O2, 5h is stirred, obtained product is washed with water into removing metal ion, then washed with decentralized medium
It washs to close to after neutrality, 100g water, ultrasonic disperse 3.5h is added；
Step 3, the product of step 1 and step 2 is mixed, is added 0.8g dibenzoyl peroxide (BPO), 4g cuts down him in Lip river
Spit of fland, stirring 10h is placed under 75 DEG C of water bath condition after prepolymerization 50min to be polymerize 22 hours in 50 DEG C of water bath with thermostatic control, with
After it is successively polymerize 5h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control afterwards, 8h is reacted in 200 DEG C of water heating kettles, is added
Enter 7g ascorbic acid, temperature is controlled at 40 DEG C, and reaction time 30h, place the product in CO2In supercritical high-pressure extraction device,
With CO2Supercritical drying 3h is carried out under temperature 45 C and air pressure 9.5MPa for medium, and the more rulers of graphene/galapectite can be obtained
Degree carries medicine aeroge.
Embodiment 6
Step 1,9g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 8g sodium styrene sulfonate, 1g poly- divinylsiloxanes (number-average molecular weight 2500, vinyl
The poly dimethyl divinylsiloxanes of the amino list sealing end of content mole percent 2%), 0.06g azodiisobutyronitrile
(ABIN), 4g dexamethasone is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 60min, 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 75 DEG C of water bath condition after prepolymerization 55min at 50 DEG C
Water bath with thermostatic control in polymerize 22 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,
It after product is washed, is scattered in 100g water, obtains galapectite and carry medicine dispersion liquid；
Step 2, by the dense H of 5g2SO4It is mixed with 7g graphite powder, 9gKMnO is added4, said mixture is placed in ice-water bath and is stirred
It mixes, maintenance system temperature is no more than 2 DEG C, sustained response 10h in whipping process, and 180g water is added, and stirs 3.5h, is cooled to room
480g water and 40gH is added in temperature2O2, 6h is stirred, obtained product is washed with water into removing metal ion, then washed with decentralized medium
It washs to close to after neutrality, 100g water, ultrasonic disperse 3.2h is added；
Step 3, the product of step 1 and step 2 is mixed, is added 1g azodiisobutyronitrile (ABIN), 2g Lovastatin stirs
It mixes 8h and is placed under 75 DEG C of water bath condition and polymerize 24 hours in 50 DEG C of water bath with thermostatic control after prepolymerization 35min, then by it
After successively distinguishing polymerase 17 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 7h is reacted in 140 DEG C of water heating kettles, and it is anti-that 10g is added
Bad hematic acid, temperature are controlled at 70 DEG C, and reaction time 40h, place the product in CO2In supercritical high-pressure extraction device, with CO2For
Medium carries out supercritical drying 3h at 38 DEG C of temperature and air pressure 10MPa, and the multiple dimensioned load medicine gas of graphene/galapectite can be obtained
Gel.
Embodiment 7
Step 1,0.5g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 0.5g sodium styrene sulfonate, the poly- divinylsiloxanes of 0.05g (number-average molecular weight 1500,
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 3.5%), 0.01g azo two is different
Butyronitrile (ABIN), 0.05g dexamethasone are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, are stirred 30min, are added to
In galapectite dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats to take out
Vacuum step three times after, after product is washed, be scattered in 100g water, be placed under 70 DEG C of water bath condition after prepolymerization 40min
It polymerize in 40 DEG C of water bath with thermostatic control 18 hours, then successively gathers it respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
It after closing 2h, after product is washed, is scattered in 100g water, obtains galapectite and carry medicine dispersion liquid；
Step 2, by the dense H of 0.5g2SO4It is mixed with 0.1g graphite powder, 0.5gKMnO is added4, said mixture is placed in ice water
It is stirred in bath, maintenance system temperature is no more than 1 DEG C, sustained response 6h in whipping process, and 50g water is added, and stirs 4h, is cooled to
350g water and 8gH is added in room temperature2O2, 3h is stirred, obtained product is washed with water into removing metal ion, then washed with decentralized medium
It washs to close to after neutrality, 100g water, ultrasonic disperse 2.5h is added；
Step 3, the product of step 1 and step 2 is mixed, is added 0.01g azodiisobutyronitrile (ABIN), 0.01g is cut down Lip river
Statin, stirring 1h is placed under 70 DEG C of water bath condition after prepolymerization 60min to be polymerize 18 hours in 40 DEG C of water bath with thermostatic control, with
After it is successively polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control afterwards, 10h is reacted in 120 DEG C of water heating kettles, is added
Enter 0.5g ascorbic acid, temperature is controlled at 100 DEG C, and reaction time 25h, place the product in CO2Supercritical high-pressure extraction device
In, with CO2Supercritical drying 4h is carried out at 30 DEG C of temperature and air pressure 15MPa for medium, and it is more that graphene/galapectite can be obtained
Scale carries medicine aeroge.
Embodiment 8
Step 1,15g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 15g sodium styrene sulfonate, 2g poly- divinylsiloxanes (number-average molecular weight 900, vinyl
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of content mole percent 4.5%), 0.5g dibenzoyl peroxide
(BPO), 10g dexamethasone is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 60min, 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 55min at 60 DEG C
Water bath with thermostatic control in polymerize 22 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,
It after product is washed, is scattered in 100g water, obtains galapectite and carry medicine dispersion liquid；
Step 2, by the dense H of 10g2SO4It is mixed with 15g graphite powder, 15gKMnO is added4, said mixture is placed in ice-water bath
Middle stirring, maintenance system temperature is no more than 3 DEG C, sustained response 10h in whipping process, and 250g water is added, and stirs 3.5h, cooling
To room temperature, 550g water and 55H is added2O2, 6h is stirred, obtained product is washed with water into removing metal ion, then use decentralized medium
100g water, ultrasonic disperse 3.2h is added to close to after neutrality in washing；
Step 3, the product of step 1 and step 2 is mixed, is added 2g dibenzoyl peroxide (BPO), 10g Lovastatin,
Stirring 8h is placed under 80 DEG C of water bath condition after prepolymerization 35min to be polymerize 24 hours in 60 DEG C of water bath with thermostatic control, then will
After it successively distinguishes polymerase 17 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 7h is reacted in 140 DEG C of water heating kettles, and 15g is added
Ascorbic acid, temperature are controlled at 70 DEG C, and reaction time 40h, place the product in CO2In supercritical high-pressure extraction device, with CO2
Supercritical drying 2h is carried out under temperature 60 C and air pressure 5MPa for medium, and the multiple dimensioned load medicine of graphene/galapectite can be obtained
Aeroge.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. graphene-galapectite aerogel composite, it is characterised in that: graphene-galapectite aerogel composite is average
Specific surface area is 600-608m2g-1, nanoscale and micro-meter scale are existed simultaneously in graphene-galapectite aerogel composite
Hole, nanoscale hole average out to 10-12nm, carries out as steps described below by 20-22 μm of average out to of micro-meter scale hole:
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 dexamethasone be added to 50 parts by weight go from
In sub- water and the mixed liquor of 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, ultrasound point
It dissipates uniformly, vacuum is kept after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, after product is washed, dispersion
In 100 parts by weight water, for warming-in-water to 70-80 DEG C of initiated polymerization, polymerization time is at least 50h, and washing is dispersed to 100
In 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 the dense H of 0.5-10 parts by weight2SO4It is mixed with 0.1-15 parts by weight of graphite powder, 0.5-15 parts by weight KMnO is added4,
Said mixture is placed in ice-water bath after being stirred to react at least 12h, 50-250 parts by weight water is added thereto, stirs evenly
Afterwards, 350-550 parts by weight water and 8-55 parts by weight H are added in Xiang Shangshu solution2O2, stir evenly, product is washed to close neutrality
Afterwards, 100 parts by weight water are added into product, ultrasonic disperse is uniform, obtains the dispersion liquid of step 2；
Step 3, after the dispersion liquid of step 1 and step 2 being mixed, 0.01-2 parts by weight initiator, 0.01-10 weight are added thereto
Part Lovastatin is measured, after mixing evenly, warming-in-water to initiated polymerization at 70-80 DEG C, after polymerization time is at least 60h,
It is added into above-mentioned reaction solution after 0.5-15 parts by weight ascorbic acid after the reaction was continued 10-40h, place the product in CO2It is overcritical
In high-pressure extraction device, with CO2Supercritical drying at least 1h is carried out at 30-60 DEG C of temperature and air pressure 5-15MPa for medium, i.e.,
Graphene-galapectite aerogel composite can be obtained.
2. according to claim 1, it is characterised in that: in step 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 parts by weight of styrene sodium sulfonate, the poly- divinyl of 0.1-1 parts by weight
Siloxanes, 0.01-0.1 parts by weight initiator, 0.1-5 parts by weight dexamethasone are added in the mixed solution of water and ethyl alcohol, stir
Above-mentioned solution is added in galapectite dispersion liquid after mixing 10-60min, ultrasonic disperse 30min, vacuum 1h is kept after vacuumizing,
Water bath with thermostatic control of the selection under 70-80 DEG C of water bath condition after prepolymerization 30-60min at 40-60 DEG C when carrying out polymerization reaction
It is then successively polymerize 2-8h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control by middle polymerization 12-24h respectively.
3. according to claim 1, it is characterised in that: in step 2, by the dense H of 1-5 parts by weight2SO4With 0.5-10 weight
Part graphite powder mixing, is added 1-10 parts by weight KMnO4, said mixture is placed in ice-water bath and is stirred, is tieed up in whipping process
Holding system temperature is 1-3 DEG C, and after sustained response 1-10h, 100-200 parts by weight water is added, stirs 1-4h, after being cooled to room temperature,
400-500 parts by weight water and 10-50 parts by weight H are added into above-mentioned solution2O2, stir 1-6h.
4. according to claim 1, it is characterised in that: in step 3,0.01-1 parts by weight are added into mixed dispersion liquid
Initiator, 0.05-5 parts by weight Lovastatin, stirring 1-10h are placed on prepolymerization 30-60min under 70-80 DEG C of water bath condition
Afterwards, exist, 12-24h is polymerize in 40-60 DEG C of water bath with thermostatic control, then by it successively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
It after polymerizeing 2-8h respectively, is placed in 80-200 DEG C of water heating kettle after reacting 1-10h, 1-10 parts by weight ascorbic acid is added thereto,
At 20-100 DEG C, supercritical drying condition is dry 2-4h under 33-55 DEG C of temperature and air pressure 7-10MPa, excellent for reaction temperature control
Select 3h.
5. according to claim 1, it is characterised in that: initiator uses dibenzoyl peroxide (BPO) or azo two
Isobutyronitrile (ABIN).
6. graphene-galapectite aerogel composite preparation method, it is characterised in that: carry out as steps described below:
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 dexamethasone be added to 50 parts by weight go from
In sub- water and the mixed liquor of 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, ultrasound point
It dissipates uniformly, vacuum is kept after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, after product is washed, dispersion
In 100 parts by weight water, for warming-in-water to 70-80 DEG C of initiated polymerization, polymerization time is at least 50h, and washing is dispersed to 100
In 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 the dense H of 0.5-10 parts by weight2SO4It is mixed with 0.1-15 parts by weight of graphite powder, 0.5-15 parts by weight KMnO is added4,
Said mixture is placed in ice-water bath after being stirred to react at least 12h, 50-250 parts by weight water is added thereto, stirs evenly
Afterwards, 350-550 parts by weight water and 8-55 parts by weight H are added in Xiang Shangshu solution2O2, stir evenly, product is washed to close neutrality
Afterwards, 100 parts by weight water are added into product, ultrasonic disperse is uniform, obtains the dispersion liquid of step 2；
Step 3, after the dispersion liquid of step 1 and step 2 being mixed, 0.01-2 parts by weight initiator, 0.01-10 weight are added thereto
Part Lovastatin is measured, after mixing evenly, warming-in-water to initiated polymerization at 70-80 DEG C, after polymerization time is at least 60h,
It is added into above-mentioned reaction solution after 0.5-15 parts by weight ascorbic acid after the reaction was continued 10-40h, place the product in CO2It is overcritical
In high-pressure extraction device, with CO2Supercritical drying at least 1h is carried out at 30-60 DEG C of temperature and air pressure 5-15MPa for medium, i.e.,
Graphene-galapectite aerogel composite can be obtained.
7. graphene according to claim 6-galapectite aerogel composite preparation method, it is characterised in that:
In step 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
Measure 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
Dexamethasone is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added to galapectite dispersion liquid after stirring 10-60min
In, ultrasonic disperse 30min keeps vacuum 1h after vacuumizing, when carrying out polymerization reaction, selection is under 70-80 DEG C of water bath condition
It polymerize 12-24h 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, 100 DEG C
Water bath with thermostatic control in polymerize 2-8h respectively.
8. graphene according to claim 6-galapectite aerogel composite preparation method, it is characterised in that:
In step 2, by the dense H of 1-5 parts by weight2SO4It is mixed with 0.5-10 parts by weight of graphite powder, 1-10 parts by weight KMnO is added4, will be above-mentioned
Mixture is placed in ice-water bath and stirs, and maintenance system temperature is 1-3 DEG C in whipping process, after sustained response 1-10h, is added
100-200 parts by weight water stirs 1-4h, and after being cooled to room temperature, 400-500 parts by weight water and 10-50 are added in Xiang Shangshu solution
Parts by weight H2O2, stir 1-6h.
9. graphene according to claim 6-galapectite aerogel composite preparation method, it is characterised in that:
In step 3,0.01-1 parts by weight initiator, 0.05-5 parts by weight Lovastatin, after stirring 1-10h are added into mixed dispersion liquid
It is placed under 70-80 DEG C of water bath condition after prepolymerization 30-60min, 12-24h is being polymerize in 40-60 DEG C of water bath with thermostatic control, then
After it is successively polymerize 2-8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, it is placed in 80-200 DEG C of water heating kettle and reacts
After 1-10h, 1-10 parts by weight ascorbic acid is added thereto, reaction temperature control is in 20-100 DEG C, supercritical drying condition
2-4h, preferably 3h are dried under 33-55 DEG C of temperature and air pressure 7-10MPa.
10. graphene according to claim 6-galapectite aerogel composite preparation method, it is characterised in that: draw
It sends out agent and uses dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
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| 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 |
| 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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| 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 |
| 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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| CN112279675A (en) * | 2020-09-30 | 2021-01-29 | 青岛理工大学 | Foam concrete based on high-stability foaming agent and preparation method thereof |
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