CN109692661A - Multiple dimensioned graphene-galapectite aerogel composite and preparation method thereof - Google Patents
Multiple dimensioned graphene-galapectite aerogel composite and preparation method thereof Download PDFInfo
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Abstract
The present invention provides multiple dimensioned graphene-galapectite aerogel composite and preparation method thereof, galapectite dispersion liquid is obtained after galapectite dispersion liquid is polymerize with the mixed solution of tetrabromobisphenol A, then prepare dense H2SO, graphite powder and KMnO4Dispersion liquid, will above two dispersion liquid mix after be added after initiator and boric acid three (2,3-dibromo) propyl ester that the reaction was continued thereto, obtain multiple dimensioned graphene-galapectite aerogel composite.It uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilize the meso-hole structure of aeroge and the microcellular structure of fiber, load tetrabromobisphenol A and boric acid three (2 respectively, 3-dibromos) propyl ester, different characteristics fire retardant is combined, realizes cooperative flame retardant effect.
Description
Technical field
The present invention relates to technical field of nano material, compound more specifically to a kind of multiple dimensioned graphene-galapectite
Aerogel material and preparation method thereof.
Background technique
Galapectite is natural one of clay mineral, belongs to kaolinic mutation, therefore also referred to as metakaolin.It is
It is crimped under field conditions (factors) by kaolinic lamella, main existence form is nanotube-shaped (Ma Zhi, king in nature
Gold leaf, Gao Xiang, Ding Tong, application study status [J] chemical progress of Qin Yongning halloysite nanotubes, 2012, (Z1): 275-
283.).Galapectite mine is distributed in each continent in the whole world, the countries such as China, France, Belgium, New Zealand, the U.S., Turkey
There are reserves abundant.Galapectite mine is mainly distributed on Guangdong, Hubei, Hunan, Sichuan, Guizhou, Yunnan, Shanxi etc. in China and saves
Part.
Galapectite is the double-deck 1:1 type aluminosilicate material, has typical crystalline texture.Galapectite is different from kaolinic
Substantive characteristics is that galapectite interlayer exists or once there is the crystallization water, and the lamella of galapectite is the oxygen-octahedron by outer layer
It is formed with the alumina octahedral regular array of internal layer, is free hydrone among lamella.These hydrones are easy to slough, this
Dehydration is irreversible.The outer surface of galapectite is mainly Si-O-Si key composition, and inner wall is then mainly aluminium hydroxyl (Niu Ji
South, Qiang Yinghuai, Wang Chunyang, Li Xiang, Monday is great, Shang Xiangyu, name, structure, pattern and the curling mechanism of Zhuan Quanchao galapectite
[J] mineral journal, 2014, (01): 13-22.).Silicon/aluminium hydroxyl is present on the crystallization edge of galapectite or the end face of pipe,
There is a small amount of embedding hydroxyl to be present in the inside of crystalline texture.Galapectite contains the water there are three types of state, mainly absorption water, crystallization
Water and chemical water.
Halloysite nanotubes have unique nanostructure, are a kind of natural nano-materials having a extensive future.And galapectite
Nanotube is widely distributed, cheap, nontoxic.Galapectite has following because of its unique nanostructure and tubular character
Advantage: firstly, it is from a wealth of sources, it is cheap；Galapectite is a kind of natural clay mineral, contains abundant, widely distributed and exploitation
It is easier to.Secondly, having good biocompatibility；Halloysite nanotubes self-assembling formation, nontoxic, biocompatibility is preferable.
In addition, active hydroxyl groups are contained in galapectite surface and interlayer, conducive to galapectite modification and further apply.Along with itself
Have the characteristics that biggish draw ratio and specific surface area, nanoscale, galapectite has obtained extensive concern and research in recent years.
The application field of halloysite nanotubes is extensive.In ceramic material, composite material, slow-release material, catalyst carrier, mould
Plate, adsorption applications etc. have a large amount of application.Because halloysite nanotubes are a kind of clay mines, it can be used for ceramic system
Make, this belongs to traditional application field of galapectite.Galapectite has the function of fiber reinforcement, is the ideal for preparing ultra-thin fine ceramics
Raw material.In recent years, the research of galapectite/polymer composites and its performance was becoming increasingly popular.Galapectite can be
Preferably disperse in most polymer composite material, mechanical property, thermal stability, anti-flammability and the knot of polymer can be effectively improved
Brilliant performance, having biggish advantage compared with other conventional fillers, (Wu Wei, Wu Pengjun, He Ding, Cao Xianwu, Zhou Nanqiao galapectite are received
Application progress [J] chemical industry progress of the mitron in high molecule nano composite material, 2011, (12): 2647-2651+2657.).
Galapectite has the characteristics that unique texture, environmental-friendly, cheap and easy to get, can prepare tool using its design feature and characterization of adsorption
There is the material of new structure and performance, is widely used in field of nanocomposite materials.
Summary of the invention
The present invention overcomes deficiencies in the prior art, provide a kind of multiple dimensioned graphene-galapectite composite aerogel
Material and preparation method thereof uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilizes airsetting
The meso-hole structure of glue and the microcellular structure of fiber, load different flame retardant respectively, and different characteristics fire retardant is combined, and realize collaboration
Flame retardant effect.
The purpose of the present invention is achieved by following technical proposals.
Multiple dimensioned graphene-galapectite aerogel composite and preparation method thereof carries out as steps described below:
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 tetrabromobisphenol A are added to 50 weight
In the mixed liquor of part deionized water and 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly,
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
Afterwards, 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
It is dispersed in 100 parts by weight water, obtains the dispersion liquid of step 1；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole hundred
Score (i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-
The poly dimethyl divinylsiloxanes of 5% amino list sealing end or the poly dimethyl divinyl silicon oxygen of amino bi-end-blocking
Alkane, 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 part by weight of boric acid three (2,3-dibromo) propyl ester, after mixing evenly, warming-in-water to initiated polymerization at 70-80 DEG C,
It is added after polymerization time is at least 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 CO2It is carried out at 31-56 DEG C of temperature and air pressure 6-12MPa for medium
Multiple dimensioned graphene-galapectite aerogel composite can be obtained in supercritical drying at least 1h.
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 tetrabromobisphenol A 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 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 part by weight of boric acid three (2,
3-dibromos) propyl ester, stirring 1-10h is placed under 70-80 DEG C of water bath condition after prepolymerization 30-60min, 40-60 DEG C
It polymerize 12-24h in water bath with thermostatic control, 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,
It 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, reaction temperature control exists
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.
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 tetrabromobisphenol A of middle addition are also dispersed in halloysite nanotubes hollow structure, Ai Luo
Stone nanotube hollow structure provides microcellular structure for multiple dimensioned graphene-galapectite aerogel composite, through vacuumizing,
After washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed inside halloysite nanotubes and are formed crosslinking knot
Tetrabromobisphenol A is supported in halloysite nanotubes by structure, and step 3 makes be located at outside halloysite nanotubes hollow structure poly- two
It polymerize under the action of initiator between vinyl functional group on vinylsiloxane, so that halloysite nanotubes and poly-
Tridimensional network is collectively formed in divinylsiloxanes, the dense H being added in step 22SO4, graphite powder and KMnO4It reacts
Graphene is formed, graphene sheet layer is successfully configured to network pore structure, above-mentioned tridimensional network and graphene film layer building
Made of network pore structure together form three-dimensional network pore structure, above-mentioned three-dimensional network pore structure is multiple dimensioned graphite
Alkene-galapectite aerogel composite provides meso-hole structure, while boric acid three (2,3-dibromo) propyl ester is supported on meso-hole structure
In.
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=-0.942/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 by relative pressure shadow
Loud function so can calculate in the hope of the aperture under different relative pressures and acquire in material that there are two
The distribution of aperture point, one kind are 10.44nm, and another kind is 20.33 μm, are measured through multiple groups, nanoscale hole is average up to 10-
11nm, micro-meter scale hole are average 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 multiple dimensioned graphene-galapectite aerogel composite N2Adsorption-desorption curve；
Fig. 2 is multiple dimensioned graphene-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 1000, ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of base content mole percent 4%), 0.02g dibenzoyl peroxide
(BPO), 0.1g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 20min, is added to Ai Luo
In stone dispersion liquid, ultrasonic disperse 25min keeps 0.5h 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 30min
It polymerize in 50 DEG C of water bath with thermostatic control 15 hours, then successively polymerize it respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After 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), 0.05g boric acid
Three (2,3-dibromo) propyl ester, stirring 2h are placed under 75 DEG C of water bath condition after prepolymerization 30min in 50 DEG C of water bath with thermostatic control
Polymerization 15 hours, after it is successively then polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, in 100 DEG C of hydro-thermals
1h is reacted in kettle, 2g ascorbic acid is added, and temperature is controlled at 60 DEG C, and reaction time 10h, place the product in CO2Overcritical height
It presses in extraction equipment, with CO2Supercritical drying 3h is carried out at 35 DEG C of temperature and air pressure 7MPa for medium, and graphite can be obtained
The multiple dimensioned carrier aeroge of alkene/galapectite.
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 3000, ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of base content mole percent 2%), 0.01g dibenzoyl peroxide
(BPO), 1g tetrabromobisphenol A 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 boric acid three
(2,3-dibromo) propyl ester, stirring 5h is placed under 75 DEG C of water bath condition after prepolymerization 40min to be gathered in 50 DEG C of water bath with thermostatic control
It closes 12 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, in 80 DEG C of water heating kettles
4h is reacted, 6g ascorbic acid is added, temperature is controlled at 20 DEG C, and reaction time 20h, place the product in CO2Supercritical, high pressure extraction
It takes in device, with CO2Supercritical drying 3h is carried out at 33 DEG C of temperature and air pressure 8MPa for medium, can be obtained graphene/angstrom
The multiple dimensioned carrier aeroge of Lip river stone.
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 2000, ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of base content mole percent 3%), 0.05g dibenzoyl peroxide
(BPO), 1.5g tetrabromobisphenol A 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 27min 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 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 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 dibenzoyl peroxide (BPO), 3g boric acid three
(2,3-dibromo) propyl ester, stirring 1h is placed under 75 DEG C of water bath condition after prepolymerization 60min to be gathered in 50 DEG C of water bath with thermostatic control
It closes 18 hours, after it is successively then polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, in 120 DEG C of water heating kettles
1g ascorbic acid is added in middle reaction 10h, and temperature is controlled at 100 DEG C, and reaction time 25h, place the product in CO2Overcritical height
It presses in extraction equipment, with CO2Supercritical drying 3h is carried out at 40 DEG C of temperature and air pressure 8.5MPa for medium, and graphite can be obtained
The multiple dimensioned carrier aeroge of alkene/galapectite.
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 4000, ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of base content mole percent 1%), 0.08g dibenzoyl peroxide
(BPO), 5g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 50min, is added to galapectite
In dispersion liquid, ultrasonic disperse 32min keeps 1.5h 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 60min 50
DEG C water bath with thermostatic control in polymerize 20 hours, it is successively then polymerize 8h 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 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 boric acid three
(2,3-dibromo) propyl ester, stirring 6h is placed under 75 DEG C of water bath condition after prepolymerization 45min to be gathered in 50 DEG C of water bath with thermostatic control
It closes 20 hours, after it is successively then polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, in 160 DEG C of water heating kettles
8g ascorbic acid is added in middle reaction 6h, and temperature is controlled at 80 DEG C, and reaction time 35h, place the product in CO2Supercritical, high pressure
In extraction equipment, with CO2Supercritical drying 3h is carried out under temperature 50 C and air pressure 9MPa for medium, can be obtained graphene/
The multiple dimensioned carrier aeroge of galapectite.
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 500, ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of base content mole percent 5%), 0.1g azodiisobutyronitrile
(ABIN), 3g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 40min, is added to galapectite
In dispersion liquid, ultrasonic disperse 29min 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 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 boric acid three (2,
3-dibromos) propyl ester, stirring 10h is placed under 75 DEG C of water bath condition to be polymerize in 50 DEG C of water bath with thermostatic control after prepolymerization 50min
22 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, in 200 DEG C of water heating kettles
8h is reacted, 7g ascorbic acid is added, temperature is controlled at 40 DEG C, and reaction time 30h, place the product in CO2Supercritical, high pressure extraction
It takes in device, with CO2Supercritical drying 3h is carried out under temperature 45 C and air pressure 9.5MPa for medium, can be obtained graphene/
The multiple dimensioned carrier aeroge of galapectite.
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 5000, vinyl
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of content mole percent 0.1%), 0.06g azodiisobutyronitrile
(ABIN), 4g tetrabromobisphenol A 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 34min 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 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 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 boric acid three (2,
3-dibromos) propyl ester, stirring 8h is placed under 75 DEG C of water bath condition to be polymerize in 50 DEG C of water bath with thermostatic control after prepolymerization 35min
24 hours, after it is successively then distinguished polymerase 17 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, in 140 DEG C of water heating kettles
7h is reacted, 10g ascorbic acid is added, temperature is controlled at 70 DEG C, and reaction time 40h, place the product in CO2Supercritical, high pressure extraction
It takes in device, with CO2Supercritical drying 3h is carried out at 38 DEG C of temperature and air pressure 10MPa for medium, can be obtained graphene/angstrom
The multiple dimensioned carrier aeroge of Lip river stone.
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 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), 0.08g tetrabromobisphenol A are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stir 10min, are added
Into galapectite dispersion liquid, ultrasonic disperse 33min keeps 1.5h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, weight
After answering 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 3 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 azodiisobutyronitrile (ABIN), 0.03g boric acid
Three (2,3-dibromo) propyl ester, stirring 5h are placed under 70 DEG C of water bath condition after prepolymerization 40min in 40 DEG C of water bath with thermostatic control
Polymerization 12 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, in 80 DEG C of water heating kettles
0.7g ascorbic acid is added in middle reaction 4h, and temperature is controlled at 20 DEG C, and reaction time 20h, place the product in CO2Overcritical height
It presses in extraction equipment, with CO2Supercritical drying 4h is carried out at 31 DEG C of temperature and air pressure 6MPa for medium, and graphite can be obtained
The multiple dimensioned carrier aeroge of alkene/galapectite.
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 2500, second
The poly dimethyl divinylsiloxanes of the amino list sealing end of amount vinyl content mole percent 1.5%), 0.4g azodiisobutyronitrile
(ABIN), 9g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 40min, is added to galapectite
In dispersion liquid, ultrasonic disperse 26min keeps 0.5h 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 80 DEG C of water bath condition after prepolymerization 50min 60
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 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 1 DEG C, sustained response 7h in whipping process, and 225g water is added, and stirs 3h, is cooled to room
520g water and 52gH 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 1.5g azodiisobutyronitrile (ABIN), 6g boric acid three (2,
3-dibromos) propyl ester, stirring 10h is placed under 80 DEG C of water bath condition to be polymerize in 60 DEG C of water bath with thermostatic control after prepolymerization 50min
22 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, in 200 DEG C of water heating kettles
8h is reacted, 12g ascorbic acid is added, temperature is controlled at 40 DEG C, and reaction time 30h, place the product in CO2Supercritical, high pressure extraction
It takes in device, with CO2Supercritical drying 2h is carried out at 56 DEG C of temperature and air pressure 12MPa for medium, can be obtained graphene/angstrom
The multiple dimensioned carrier aeroge of Lip river stone.
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. multiple dimensioned graphene-galapectite aerogel composite, it is characterised in that: graphene-galapectite composite aerogel material
Material average specific surface area is 601-605m2g-1, nanoscale and micro- is existed simultaneously in graphene-galapectite aerogel composite
Metrical scale hole, nanoscale hole average out to 10-11nm, 20-21 μm of average out to of micro-meter scale hole, as steps described below into
Row:
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 tetrabromobisphenol A are added to 50 parts by weight and go
In ionized water and the mixed liquor of 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, ultrasound
It is uniformly dispersed, vacuum is kept after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, after product is washed, point
It dissipates 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 dispersion
Into 100 parts by weight water, the dispersion liquid of step 1 is obtained；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole percent
(i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-5%'s
The poly dimethyl divinylsiloxanes of amino list sealing end or the poly dimethyl divinylsiloxanes of amino bi-end-blocking；
Step 2, by 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
Part by weight of boric acid three (2,3-dibromo) propyl ester, after mixing evenly, warming-in-water to initiated polymerization at 70-80 DEG C, when polymerization
Between be at least 60h after, be added in Xiang Shangshu reaction solution after 0.7-12 parts by weight ascorbic acid after the reaction was continued 10-40h, by product
It is placed in CO2In supercritical high-pressure extraction device, with CO2It is carried out at 31-56 DEG C of temperature and air pressure 6-12MPa for medium overcritical
Dry at least 1h, can be obtained multiple dimensioned graphene-galapectite aerogel composite.
2. multiple dimensioned graphene-galapectite aerogel composite according to claim 1, it is characterised in that: in step 1
In, 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
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 tetrabromo
Bisphenol-A is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added in galapectite dispersion liquid after stirring 10-60min,
Ultrasonic disperse 25-35min keeps vacuum 0.5-2h, water-bath item of the selection at 70-80 DEG C when carrying out polymerization reaction after vacuumizing
It polymerize 12-24h under part after prepolymerization 30-60min in 40-60 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C,
It polymerize 2-8h respectively in 100 DEG C of water bath with thermostatic control.
3. multiple dimensioned graphene-galapectite aerogel composite according to claim 1, it is characterised in that: in step 2
In, 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, by said mixture
It is placed in ice-water bath and stirs, maintenance system temperature is 1-3 DEG C in whipping process, and after sustained response 1-10h, 100-200 is added
Parts by weight water stirs 1-4h, and after being cooled to room temperature, 400-500 parts by weight water and 10-50 parts by weight are added in Xiang Shangshu solution
H2O2, stir 1-6h.
4. multiple dimensioned graphene-galapectite aerogel composite according to claim 1, it is characterised in that: in step 3
In, 0.01-1 parts by weight initiator is added into mixed dispersion liquid, 0.05-5 part by weight of boric acid three (2,3-dibromo) propyl ester stirs
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. multiple dimensioned graphene-galapectite aerogel composite according to claim 1, it is characterised in that: initiator
Using dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
6. multiple dimensioned graphene-galapectite aerogel composite preparation method, it is characterised in that: as steps described below into
Row:
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 tetrabromobisphenol A are added to 50 parts by weight and go
In ionized water and the mixed liquor of 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, ultrasound
It is uniformly dispersed, vacuum is kept after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, after product is washed, point
It dissipates 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 dispersion
Into 100 parts by weight water, the dispersion liquid of step 1 is obtained；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole percent
(i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-5%'s
The poly dimethyl divinylsiloxanes of amino list sealing end or the poly dimethyl divinylsiloxanes of amino bi-end-blocking；
Step 2, by 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
Part by weight of boric acid three (2,3-dibromo) propyl ester, after mixing evenly, warming-in-water to initiated polymerization at 70-80 DEG C, when polymerization
Between be at least 60h after, be added in Xiang Shangshu reaction solution after 0.7-12 parts by weight ascorbic acid after the reaction was continued 10-40h, by product
It is placed in CO2In supercritical high-pressure extraction device, with CO2It is carried out at 31-56 DEG C of temperature and air pressure 6-12MPa for medium overcritical
Dry at least 1h, can be obtained multiple dimensioned graphene-galapectite aerogel composite.
7. the preparation method of multiple dimensioned graphene-galapectite aerogel composite according to claim 6, feature exist
In: 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, it will
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 tetrabromobisphenol A is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added to Ai Luo after stirring 10-60min
In stone dispersion liquid, ultrasonic disperse 25-35min keeps vacuum 0.5-2h after vacuumizing, when carrying out polymerization reaction, selection is in 70-
It polymerize 12-24h in 40-60 DEG C of water bath with thermostatic control after prepolymerization 30-60min under 80 DEG C of water bath condition, then successively by it
It polymerize 2-8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control.
8. the preparation method of multiple dimensioned graphene-galapectite aerogel composite according to claim 6, feature exist
In: 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
Said 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, adds
Enter 100-200 parts by weight water, stir 1-4h, after being cooled to room temperature, 400-500 parts by weight water and 10- are added in Xiang Shangshu solution
50 parts by weight H2O2, stir 1-6h.
9. the preparation method of multiple dimensioned graphene-galapectite aerogel composite according to claim 6, feature exist
In: in step 3,0.01-1 parts by weight initiator, 0.05-5 part by weight of boric acid three (2,3-two are added into mixed dispersion liquid
Bromine) propyl ester, stirring 1-10h is placed under 70-80 DEG C of water bath condition after prepolymerization 30-60min, in 40-60 DEG C of thermostatted water
It polymerize 12-24h in 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. the preparation method of multiple dimensioned graphene-galapectite aerogel composite according to claim 6, feature
Be: initiator uses dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
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| US4954327A (en) * | 1988-08-12 | 1990-09-04 | Blount David H | Production of silica aerogels |
| CN101372620A (en) * | 2008-09-25 | 2009-02-25 | 河南省科学院 | Galapectite load antimony pentoxide nano complex and preparation thereof |
| CN105273727A (en) * | 2015-11-25 | 2016-01-27 | 北京旭碳新材料科技有限公司 | Composition for flame-retardant composite material and graphene oxide flame-retardant film as well as preparation method and application of graphene oxide flame-retardant film |
| 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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2017
- 2017-10-20 CN CN201710986539.2A patent/CN109692661A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954327A (en) * | 1988-08-12 | 1990-09-04 | Blount David H | Production of silica aerogels |
| CN101372620A (en) * | 2008-09-25 | 2009-02-25 | 河南省科学院 | Galapectite load antimony pentoxide nano complex and preparation 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 |
| CN105273727A (en) * | 2015-11-25 | 2016-01-27 | 北京旭碳新材料科技有限公司 | Composition for flame-retardant composite material and graphene oxide flame-retardant film as well as preparation method and application of graphene oxide flame-retardant film |
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