CN109694448A - With mesoporous and micropore graphene net-galapectite aerogel composite and preparation method thereof - Google Patents
With mesoporous and micropore graphene net-galapectite aerogel composite and preparation method thereof Download PDFInfo
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Abstract
The present invention provides the graphene net-galapectite aerogel composite and preparation method thereof with mesoporous and micropore, galapectite dispersion liquid is obtained after galapectite dispersion liquid is polymerize with the mixed solution of deca-BDE, then prepare dense H2SO, graphite powder and KMnO4Dispersion liquid, will above two dispersion liquid mix after be added after initiator and ammonium polyphosphate that the reaction was continued thereto, obtain graphene-galapectite aerogel composite.It uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, using the meso-hole structure of aeroge and the microcellular structure of fiber, load deca-BDE and ammonium polyphosphate respectively, different characteristics fire retardant is combined, realize cooperative flame retardant effect.
Description
Technical field
The present invention relates to technical field of nano material, more specifically to a kind of with mesoporous and micropore netted stone
Black alkene-galapectite aerogel composite 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 with mesoporous and micropore graphene net-angstrom
Lip river stone aerogel composite and preparation method thereof, uses the doughnut with microcellular structure for raw material, builds three-dimensional airsetting
Glue network loads different flame retardant using the meso-hole structure of aeroge and the microcellular structure of fiber respectively, and different characteristics are fire-retardant
Agent combines, and realizes cooperative flame retardant effect.
The purpose of the present invention is achieved by following technical proposals.
With mesoporous and micropore graphene net-galapectite aerogel composite and preparation method thereof, according to following
Step carries out:
Step 1,0.6-12 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, galapectite dispersion liquid is obtained, by 0.6-12 parts by weight of styrene sodium sulfonate, 0.06-1.8
The poly- divinylsiloxanes of parts by weight, 0.01-0.4 parts by weight initiator, 0.08-9 parts by weight deca-BDE are added to 50 weights
In the mixed liquor for measuring part deionized water and 50 parts by weight of ethanol, above-mentioned solution is added to galapectite dispersion liquid after mixing evenly
In, ultrasonic disperse is uniform, and vacuum is kept after vacuumizing, and is then restored to normal pressure, and after repeating vacuum step three times, product is washed
It after washing, is scattered in 100 parts by weight water, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization time is at least 50h, washes
It washs and is dispersed in 100 parts by weight water, obtain 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, poly- divinylsiloxanes are purchased from Dow corning company.
Step 2, by the dense H of 0.8-8 parts by weight2SO4It is mixed with 0.3-12 parts by weight of graphite powder, 0.6-12 parts by weight is added
KMnO4, said mixture is placed in ice-water bath after being stirred to react at least 12h, 75-225 parts by weight water, stirring is added thereto
After uniformly, 360-520 parts by weight water and 9-52 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, 0.01-1.5 parts by weight initiator is added thereto,
0.03-6 parts by weight ammonium polyphosphate, after mixing evenly, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization time is at least
It is added after 60h, in Xiang Shangshu reaction solution after 0.7-12 parts by weight ascorbic acid after the reaction was continued 10-40h, place the product in
CO2In supercritical high-pressure extraction device, with CO2Supercritical drying is carried out at 31-56 DEG C of temperature and air pressure 6-12MPa for medium
At least 1h can be obtained with mesoporous and micropore graphene net-galapectite aerogel composite.
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 deca-BDE is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added after stirring 10-60min
Into galapectite dispersion liquid, ultrasonic disperse 25-35min keeps vacuum 0.5-2h 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 ammonium polyphosphate,
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 deca-BDE of middle addition are also dispersed in halloysite nanotubes hollow structure, angstrom
Lip river stone nanotube hollow structure is provides micropore knot with mesoporous and micropore graphene net-galapectite aerogel composite
Structure, after vacuumizing, washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, form galapectite nanometer
Cross-linked structure is formed inside pipe, deca-BDE is supported in halloysite nanotubes, and step 3 to be located at halloysite nanotubes
It polymerize under the action of initiator between the vinyl functional group in poly- divinylsiloxanes outside hollow structure, so that
Tridimensional network is collectively formed in halloysite nanotubes and poly- divinylsiloxanes, the dense H being added in step 22SO4, graphite powder
With KMnO4React to form graphene, graphene sheet layer is successfully configured to network pore structure, above-mentioned tridimensional network with
The built-up network pore structure of graphene sheet layer together forms three-dimensional network pore structure, above-mentioned three-dimensional network hole knot
Structure is provides meso-hole structure with mesoporous and micropore graphene net-galapectite aerogel composite, while by polyphosphoric acid
Ammonium 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, surveys through multiple groups
The average specific surface area for measuring material is 601-605m2g-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=-0.965/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.366 [- 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
10.48nm, another kind are 20.68 μm, are measured through multiple groups, and nanoscale hole is average up to 10-11nm, and micro-meter scale hole is flat
Up to 20-21 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.
Detailed description of the invention
Fig. 1 is that have mesoporous and micropore graphene net-galapectite aerogel composite N2Adsorption-desorption is bent
Line；
Fig. 2 is that have mesoporous and micropore graphene net-galapectite aerogel composite electromicroscopic photograph.
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 0.1%), 0.02g diphenyl peroxide first
Acyl (BPO), 0.1g deca-BDE are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, are stirred 20min, are added to angstrom
In the stone dispersion liquid of Lip river, ultrasonic disperse 25min keeps 0.5h 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 75 DEG C of water bath condition after prepolymerization 30min
It polymerize in 50 DEG C of water bath with thermostatic control 15 hours, then successively gathers it respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After closing 5h, after product is washed, it is scattered in 100g water, obtains galapectite support dispersion；
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), the poly- phosphorus of 0.05g
Sour ammonium, 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
Carrier 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 500, ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of base content mole percent 5%), 0.01g dibenzoyl peroxide
(BPO), 1g deca-BDE 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 35min keeps 2h 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 support dispersion；
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 dibenzoyl peroxide (BPO), 1g polyphosphoric acid
Ammonium, 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 3.5h is carried out at 33 DEG C of temperature and air pressure 8MPa for medium, and the multiple dimensioned load of graphene/galapectite can be obtained
Body 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 deca-BDE is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 30min, is added to angstrom
In the stone dispersion liquid of Lip river, ultrasonic disperse 28min keeps 1.5h 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 75 DEG C of water bath condition after prepolymerization 40min
It polymerize in 50 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
After closing 2h, after product is washed, it is scattered in 100g water, obtains galapectite support dispersion；
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 50gH2O2 is added in temperature, stirs 3h, obtained product is washed with water 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 ammonium polyphosphate,
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 2.5h is carried out at 40 DEG C of temperature and air pressure 8.5MPa for medium, and it is multiple dimensioned that graphene/galapectite can be obtained
Carrier 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 azodiisobutyronitrile
(ABIN), 5g deca-BDE is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 50min, is added to Ai Luo
In stone dispersion liquid, ultrasonic disperse 27min keeps 1.5h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats to take out true
Empty 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 60min
It polymerize in 50 DEG C of water bath with thermostatic control 20 hours, then successively polymerize it respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After 8h, after product is washed, it is scattered in 100g water, obtains galapectite support dispersion；
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 azodiisobutyronitrile (ABIN), 5g ammonium polyphosphate,
Stirring 6h is placed under 75 DEG C of water bath condition after prepolymerization 45min to be polymerize 20 hours in 50 DEG C of water bath with thermostatic control, then will
After it successively polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 6h is reacted in 160 DEG C of water heating kettles, and 8g is added
Ascorbic acid, temperature are controlled at 80 DEG C, and reaction time 35h, place the product in CO2In supercritical high-pressure extraction device, with CO2
Supercritical drying 2h is carried out under temperature 50 C and air pressure 9MPa for medium, and the multiple dimensioned carrier of graphene/galapectite can be obtained
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 list sealing end of amount vinyl content mole percent 1.5%), 0.1g azodiisobutyronitrile
(ABIN), 3g deca-BDE is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 40min, 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 50min 50
DEG C water bath with thermostatic control in polymerize 24 hours, it is successively then polymerize 4h 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 support dispersion；
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 azodiisobutyronitrile (ABIN), 4g ammonium polyphosphate,
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, then will
After it successively polymerize 5h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 8h is reacted in 200 DEG C of water heating kettles, and 7g is added
Ascorbic acid, temperature are controlled at 40 DEG C, and reaction time 30h, place the product in CO2In supercritical high-pressure extraction device, with CO2
Supercritical drying 3h is carried out under temperature 45 C and air pressure 9.5MPa for medium, and the multiple dimensioned load of graphene/galapectite can be obtained
Body 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 bi-end-blocking of content mole percent 2%), 0.06g azodiisobutyronitrile
(ABIN), 4g deca-BDE is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 60min, 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 55min 50
DEG C water bath with thermostatic control in polymerize 22 hours, it is then successively distinguished in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control to polyase 13 h
Afterwards, it after product being washed, is scattered in 100g water, obtains galapectite support dispersion；
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 ammonium polyphosphate is stirred
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 1h at 38 DEG C of temperature and air pressure 10MPa, and the multiple dimensioned carrier gas of graphene/galapectite can be obtained
Gel.
Embodiment 7
Step 1,0.6g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 0.6g sodium styrene sulfonate, the poly- divinylsiloxanes of 0.06g (number-average molecular weight 3500,
The poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 2.5%), 0.01g peroxidating two
Benzoyl (BPO), 0.08g deca-BDE are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, are stirred 10min, are added
Entering into galapectite dispersion liquid, ultrasonic disperse 26min keeps 0.5h, is then restored to normal pressure after vacuumizing above-mentioned mixed liquor,
After repeating vacuum step three times, after product is washed, it is scattered in 100g water, is placed in prepolymerization under 70 DEG C of water bath condition
It polymerize 12 hours after 35min in 40 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
After polymerizeing 6h respectively, after product is washed, it is scattered in 100g water, obtains galapectite support dispersion；
Step 2, by the dense H of 0.8g2SO4It is mixed with 0.3g graphite powder, 0.6gKMnO 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 4h in whipping process, and 75g water is added, and stirs 2h, is cooled to
360g water and 9gH is added in room temperature2O2, 2h 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 4h is added；
Step 3, the product of step 1 and step 2 is mixed, is added 0.01g dibenzoyl peroxide (BPO), the poly- phosphorus of 0.03g
Sour ammonium, stirring 5h is placed under 70 DEG C of water bath condition after prepolymerization 40min to be polymerize 12 hours in 40 DEG C of water bath with thermostatic control, with
After it is successively distinguished polyase 13 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control afterwards, 4h is reacted in 80 DEG C of water heating kettles, is added
0.7g ascorbic acid, temperature are controlled at 20 DEG C, and reaction time 20h, place the product in CO2In supercritical high-pressure extraction device,
With CO2Supercritical drying 4h is carried out at 31 DEG C of temperature and air pressure 6MPa for medium, and it is multiple dimensioned that graphene/galapectite can be obtained
Carrier aeroge.
Embodiment 8
Step 1,12g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse
1h obtains galapectite dispersion liquid, by 12g sodium styrene sulfonate, 1.8g poly- divinylsiloxanes (number-average molecular weight 1500, second
The poly dimethyl divinylsiloxanes of the amino list sealing end of amount vinyl content mole percent 3%), 0.4g dibenzoyl peroxide
(BPO), 9g deca-BDE 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 32min keeps 2h 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 support dispersion；
Step 2, by the dense H of 8g2SO4It is mixed with 12g graphite powder, 12gKMnO is added4, said mixture is placed in ice-water bath
Stirring, maintenance system temperature is no more than 3 DEG C, sustained response 10h in whipping process, and 225g water is added, and stirs 3.5h, is cooled to
520g water and 52gH is added in room temperature2O2, 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 1.5g dibenzoyl peroxide (BPO), 6g polyphosphoric acid
Ammonium, stirring 8h is placed under 80 DEG C of water bath condition after prepolymerization 35min polymerize 24 hours in 60 DEG C of water bath with thermostatic control, then
After it is successively distinguished 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, is added
12g ascorbic acid, temperature are controlled at 70 DEG C, and reaction time 40h, place the product in CO2In supercritical high-pressure extraction device, with
CO2Supercritical drying 2h is carried out at 56 DEG C of temperature and air pressure 12MPa for medium, and it is multiple dimensioned that graphene/galapectite can be obtained
Carrier aeroge.
Flame retardant property test:
The material and EVA (mass ratio 1:4) for taking the method for the invention to prepare, are warming up to 140 DEG C for mixer, 45
EVA is added under conditions of rev/min, the material of invention the method preparation is added after constant torque, keeps 10min to mixing
Uniformly.Composite material after mixing is put into vulcanizing press, sample processed is molded with 140 DEG C of 10MPa, is placed on dry and ventilated
Place is for 24 hours.According to GB/T2406.2-2009, GB8624-2006 and document (Li Bin, Wang Jianqi, polymer material flammability and resistance
Evaluation --- cone calorimetry (CONE) method of combustion property, polymer material science and engineering, 1998,14:15) the method measurement
Composite material limit oxygen index, maximum heatrelease rate and ignitor firing time, the results are shown in Table 1.
The flame retardant property of 1 material of table
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. with mesoporous and micropore graphene net-galapectite aerogel composite, it is characterised in that: graphene-Ai Luo
Stone aerogel composite average specific surface area is 601-605m2g-1, deposited in graphene-galapectite aerogel composite simultaneously
In nanoscale and micro-meter scale hole, nanoscale hole average out to 10-11nm, 20-21 μm of average out to of micro-meter scale hole,
It carries out as steps described below:
Step 1,0.6-12 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 0.6-12 parts by weight of styrene sodium sulfonate, 0.06-1.8 weight
The poly- divinylsiloxanes of part, 0.01-0.4 parts by weight initiator, 0.08-9 parts by weight deca-BDE are 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 initiated polymerization at 70-80 DEG C, polymerization time is at least 50h, washing point
It is dissipated 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 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 0.8-8 parts by weight2SO4It is mixed with 0.3-12 parts by weight of graphite powder, 0.6-12 parts by weight KMnO is added4,
Said mixture is placed in ice-water bath after being stirred to react at least 12h, 75-225 parts by weight water is added thereto, stirs evenly
Afterwards, 360-520 parts by weight water and 9-52 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, 0.01-1.5 parts by weight initiator, 0.03-6 are added thereto
Parts by weight ammonium polyphosphate, 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 0.7-12 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 31-56 DEG C of temperature and air pressure 6-12MPa for medium,
It can be obtained with mesoporous and micropore graphene net-galapectite aerogel composite.
2. it is according to claim 1 with mesoporous and micropore graphene net-galapectite aerogel composite, it is special
Sign is: in step 1,1-10 parts by weight halloysite nanotubes being 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 deca-BDE is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added after stirring 10-60min
Into galapectite dispersion liquid, ultrasonic disperse 25-35min keeps vacuum 0.5-2h, the selection when carrying out polymerization reaction after vacuumizing
It polymerize 12-24h after prepolymerization 30-60min in 40-60 DEG C of water bath with thermostatic control under 70-80 DEG C of water bath condition, then by it
Successively it polymerize 2-8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control.
3. it is according to claim 1 with mesoporous and micropore graphene net-galapectite aerogel composite, it is special
Sign is: 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.
4. it is according to claim 1 with mesoporous and micropore graphene net-galapectite aerogel composite, it is special
Sign is: in step 3,0.01-1 parts by weight initiator being added into mixed dispersion liquid, 0.05-5 parts by weight ammonium polyphosphate is stirred
It mixes 1-10h to be placed under 70-80 DEG C of water bath condition after prepolymerization 30-60min, 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.
5. it is according to claim 1 with mesoporous and micropore graphene net-galapectite aerogel composite, it is special
Sign is: initiator uses dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
6. with mesoporous and micropore graphene net-galapectite aerogel composite preparation method, it is characterised in that: press
It is carried out according to following step:
Step 1,0.6-12 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 0.6-12 parts by weight of styrene sodium sulfonate, 0.06-1.8 weight
The poly- divinylsiloxanes of part, 0.01-0.4 parts by weight initiator, 0.08-9 parts by weight deca-BDE are 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 initiated polymerization at 70-80 DEG C, polymerization time is at least 50h, washing point
It is dissipated 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 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 0.8-8 parts by weight2SO4It is mixed with 0.3-12 parts by weight of graphite powder, 0.6-12 parts by weight KMnO is added4,
Said mixture is placed in ice-water bath after being stirred to react at least 12h, 75-225 parts by weight water is added thereto, stirs evenly
Afterwards, 360-520 parts by weight water and 9-52 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, 0.01-1.5 parts by weight initiator, 0.03-6 are added thereto
Parts by weight ammonium polyphosphate, 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 0.7-12 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 31-56 DEG C of temperature and air pressure 6-12MPa for medium,
It can be obtained with mesoporous and micropore graphene net-galapectite aerogel composite；
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 deca-BDE entered is also dispersed in halloysite nanotubes hollow structure, galapectite
Nanotube hollow structure to provide microcellular structure with mesoporous and micropore graphene net-galapectite aerogel composite,
After vacuumizing, washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed in halloysite nanotubes
Portion forms cross-linked structure, and deca-BDE is supported in halloysite nanotubes, and step 3 makes hollow positioned at halloysite nanotubes
It polymerize under the action of initiator between the vinyl functional group in poly- divinylsiloxanes outside structure, so that angstrom Lip river
Tridimensional network is collectively formed in stone nanotube and poly- divinylsiloxanes, the dense H being added in step 22SO4, graphite powder with
KMnO4It reacts to form graphene, graphene sheet layer is successfully configured to network pore structure, above-mentioned tridimensional network and stone
The built-up network pore structure of black alkene lamella together forms three-dimensional network pore structure, above-mentioned three-dimensional network pore structure
To provide meso-hole structure with mesoporous and micropore graphene net-galapectite aerogel composite, while by ammonium polyphosphate
It is supported in meso-hole structure.
7. according to claim 6 with mesoporous and micropore graphene net-galapectite aerogel composite system
Preparation Method, it is characterised in that: in step 1,1-10 parts by weight halloysite nanotubes are added to the mixed solution of water and ethyl alcohol
Middle ultrasonic disperse 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 weight
Part initiator is measured, 0.1-5 parts by weight deca-BDE is added in the mixed solution of water and ethyl alcohol, will be upper after stirring 10-60min
It states solution to be added in galapectite dispersion liquid, ultrasonic disperse 25-35min, vacuum 0.5-2h is kept after vacuumizing, is being polymerize
Selection polymerize 12- in 40-60 DEG C of water bath with thermostatic control after prepolymerization 30-60min under 70-80 DEG C of water bath condition when reaction
For 24 hours, it is successively then polymerize 2-8h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively.
8. according to claim 6 with mesoporous and micropore graphene net-galapectite aerogel composite system
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- is added
10 parts by weight KMnO4, said mixture is placed in ice-water bath and is stirred, maintenance system temperature is 1-3 DEG C in whipping process, is held
After continuous reaction 1-10h, 100-200 parts by weight water is added, stirs 1-4h, after being cooled to room temperature, 400- is added in Xiang Shangshu solution
500 parts by weight water and 10-50 parts by weight H2O2, stir 1-6h.
9. according to claim 6 with mesoporous and micropore graphene net-galapectite aerogel composite system
Preparation Method, it is characterised in that: in step 3,0.01-1 parts by weight initiator, 0.05-5 parts by weight are added into mixed dispersion liquid
Ammonium polyphosphate, stirring 1-10h is placed under 70-80 DEG C of water bath condition after prepolymerization 30-60min, in 40-60 DEG C of constant temperature
It polymerize 12-24h in water-bath, 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, is placed in
After reacting 1-10h in 80-200 DEG C of water heating kettle, 1-10 parts by weight ascorbic acid is added thereto, reaction temperature is controlled in 20-100
DEG C, supercritical drying condition is dry 2-4h, preferably 3h under 33-55 DEG C of temperature and air pressure 7-10MPa.
10. according to claim 6 with mesoporous and micropore graphene net-galapectite aerogel composite system
Preparation Method, it is characterised in that: initiator uses dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
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