CN109692633A - Fire-retardant carbon nanotube-galapectite aerogel composite and preparation method thereof - Google Patents
Fire-retardant carbon nanotube-galapectite aerogel composite and preparation method thereof Download PDFInfo
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Abstract
The present invention provides fire-retardant carbon nanotube-galapectite aerogel composite and preparation method thereof, galapectite dispersion liquid is obtained after galapectite dispersion liquid is polymerize with the mixed solution of hexabromocyclododecane, the wet gel of lauryl sodium sulfate and carbon nanotube is prepared again, initiator and bis-phenol bis- (diphenyl phosphates) is added after dispersion liquid is mixed with wet gel thereto, and the reaction was continued afterwards, obtains fire-retardant carbon nanotube-galapectite aerogel composite.Use the doughnut with microcellular structure for raw material, three-dimensional aeroge network is built, using the meso-hole structure of aeroge and the microcellular structure of fiber, hexabromocyclododecane is loaded respectively and bis-phenol is bis- (diphenyl phosphate), 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 fire-retardant carbon nanotube-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 fire-retardant carbon nanotube-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.
Fire-retardant carbon nanotube-galapectite aerogel composite and preparation method thereof carries out as steps described below:
Step 1,0.7-12 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 0.7-12 parts by weight of styrene sodium sulfonate, 0.06-1.6
The poly- divinylsiloxanes of parts by weight, 0.01-0.3 parts by weight initiator, 0.08-8 parts by weight hexabromocyclododecane are added to 50
In the mixed liquor of parts by weight of 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 reaction time at least 50h,
Washing is dispersed in 100 parts by weight water, obtains the dispersion liquid of step 1；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole hundred
Score (i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-
The poly dimethyl divinylsiloxanes of 5% amino list sealing end or the poly dimethyl divinyl silicon oxygen of amino bi-end-blocking
Alkane is purchased from Dow corning company.
Step 2,0.6-12 parts by weight lauryl sodium sulfate is taken to be added in 100 parts by weight water, after sonic oscillation, thereto
The carbon nanotube of 0.6-12 parts by weight is added, after ultrasonic disperse is uniform, vacuum is kept after vacuumizing, is then restored to normal pressure, weight
Multiple vacuum step three times, obtains the wet gel of step 2；
Step 3, the dispersion liquid of 0.8-12 parts by weight step 1 is mixed with the wet gel of 0.7-22 parts by weight step 2, Xiang Qi
Middle addition 0.01-1.2 parts by weight initiator, 0.03-7 parts by weight of bisphenol is bis- (diphenyl phosphate), after ultrasonic disperse is uniform, water-bath
It is warming up to initiated polymerization at 70-80 DEG C, after polymerization reaction time at least 50h, product is freeze-dried, drying time is at least
2h obtains carbon nanotube-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 hexabromocyclododecane is added in the mixed solution of water and ethyl alcohol, adds above-mentioned solution after stirring 10-60min
Enter into galapectite dispersion liquid, ultrasonic disperse 25-35min, vacuum 0.5-1.5h is kept after vacuumizing, when carrying out polymerization reaction
Selection polymerize 12-24h in 40-60 DEG C of water bath with thermostatic control after prepolymerization 30-60min under 70-80 DEG C of water bath condition, then
It is successively polymerize 2-8h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively.
In step 2,1-10 parts by weight lauryl sodium sulfate is added to the water, after sonic oscillation 2-48h, thereto plus
Enter the carbon nanotube of 1-10 parts by weight, after the uniform 1-24h of ultrasonic disperse, vacuum 1h is kept after vacuumizing.
In step 3, the dispersion liquid of 1-10 parts by weight step 1 is mixed with the wet gel of 1-20 parts by weight step 2, Xiang Qi
Middle addition 0.01-1 parts by weight initiator, 0.05-5 parts by weight of bisphenol is bis- (diphenyl phosphate), after ultrasonic disperse is uniform, is carrying out
Selection polymerize 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 polymerization reaction
It, is then successively polymerize 2-8h by 12-24h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, and freeze-drying condition is temperature
- 6 DEG C of degree -- 105 DEG C, 2-55 DEG C of humidity, vacuum degree 10-50000pa, time 2-48h.
Initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
Positive charge is had on the inside of halloysite nanotubes tube wall, and negative electrical charge, the styrene being added in step 1 are had on the outside of tube wall
Sodium sulfonate has negative electrical charge, and sodium styrene sulfonate is adsorbed on halloysite nanotubes inner wall by electrostatic interaction, while in step 1
Poly- divinylsiloxanes, initiator and the hexabromocyclododecane of middle addition are also dispersed in halloysite nanotubes hollow structure,
Halloysite nanotubes hollow structure provides microcellular structure for fire-retardant carbon nanotube-galapectite aerogel composite, by taking out
After vacuum, washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed to be formed inside halloysite nanotubes and be handed over
It is coupled structure, hexabromocyclododecane is supported in halloysite nanotubes, step 3 to be located at outside halloysite nanotubes hollow structure
Poly- divinylsiloxanes on vinyl functional group between polymerize under the action of initiator so that galapectite nanometer
Tridimensional network is collectively formed in pipe and poly- divinylsiloxanes, and the carbon nanotube being added in step 2 is successfully configured to network
Pore structure, above-mentioned tridimensional network and carbon nanotube are successfully configured to network pore structure and together form three-dimensional network hole
Gap structure, above-mentioned three-dimensional network pore structure provide meso-hole structure for fire-retardant carbon nanotube-galapectite aerogel composite, together
When bis-phenol bis- (diphenyl phosphates) 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 606.44m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, surveys through multiple groups
The average specific surface area for measuring material is 604-609m2g-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=-0.958/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
10.22nm, another kind are 17.51 μm, are measured through multiple groups, and nanoscale hole is average up to 10-12nm, and micro-meter scale hole is flat
Up to 15-18 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 carbon nano-tube fibre successfully constructs
For network pore structure, aperture size is in mesoporous scale.It is overlapped to form three-dimensional netted halloysite nanotubes and is uniformly dispersed in carbon
In nanotube three-dimensional network hole, the building of dual load system is realized.
Detailed description of the invention
Fig. 1 is fire-retardant carbon nanotube-galapectite aerogel composite N2Adsorption-desorption curve；
Fig. 2 is fire-retardant carbon nanotube-galapectite aerogel composite electromicroscopic photograph.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1
1g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 2g sodium styrene sulfonate, 0.2g poly- divinylsiloxanes (number-average molecular weight 4000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of mole percent 1%), 0.01g dibenzoyl peroxide (BPO),
3g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 10min, is added to galapectite dispersion
In liquid, ultrasonic disperse 25min keeps 1.5h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats vacuum step
It after three times, after product is washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 35min at 50 DEG C
It polymerize 12 hours in water bath with thermostatic control, it, will after it is successively then polymerize 4h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After product washing, it is scattered in 100g water, obtains galapectite support dispersion；Take 1g lauryl sodium sulfate that 100g water is added
In, after sonic oscillation 2h, the carbon nanotube of 4g is added, ultrasonic disperse 1h obtains dispersion liquid；It is protected after above-mentioned dispersion liquid is vacuumized
1h is held, normal pressure is then restored to, vacuum step is repeated three times, obtains carbon nanotube carrier wet gel；By 2g galapectite carrier
Dispersion liquid is mixed with 1g carbon nanotube carrier wet gel, is added 0.5g dibenzoyl peroxide (BPO), the bis- (phosphoric acid of 0.05g bis-phenol
Diphenyl ester), re-ultrasonic dispersion 2h is placed under 75 DEG C of water bath condition and polymerize in 50 DEG C of water bath with thermostatic control after prepolymerization 30min
14 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, product is freeze-dried,
Cryogenic temperature is -6 DEG C, and dry humidity is 2 DEG C, and dry vacuum degree is generally 2000pa, and drying time is generally 2 hours, obtains
The multiple dimensioned carrier aeroge of carbon nanotube/galapectite.
Embodiment 2
4g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 1g sodium styrene sulfonate, 0.5g poly- divinylsiloxanes (number-average molecular weight 1500, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 2.5%), 0.04g azodiisobutyronitrile (ABIN),
4g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 30min, is added to galapectite dispersion
In liquid, ultrasonic disperse 35min keeps 0.5h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats vacuum step
It after three times, after product is washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 30min at 50 DEG C
It polymerize 14 hours in water bath with thermostatic control, it, will after it is successively then polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After product washing, it is scattered in 100g water, obtains galapectite support dispersion；Take 2g lauryl sodium sulfate that 100g water is added
In, after sonic oscillation 48h, the carbon nanotube of 10g is added, ultrasonic disperse 4h obtains dispersion liquid；After above-mentioned dispersion liquid is vacuumized
1h is kept, normal pressure is then restored to, vacuum step is repeated three times, obtains carbon nanotube carrier wet gel；4g galapectite is carried
Dispersion liquid is mixed with 5g carbon nanotube carrier wet gel, is added 0.01g azodiisobutyronitrile (ABIN), the bis- (phosphoric acid of 1g bis-phenol
Diphenyl ester), re-ultrasonic dispersion 10h is placed under 75 DEG C of water bath condition and polymerize in 50 DEG C of water bath with thermostatic control after prepolymerization 40min
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, product is freeze-dried,
Cryogenic temperature is -105 DEG C, and dry humidity is 20 DEG C, and dry vacuum degree is generally 10pa, and drying time is generally 48 hours, obtains
To the multiple dimensioned carrier aeroge of carbon nanotube/galapectite.
Embodiment 3
6g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 6g sodium styrene sulfonate, 0.1g poly- divinylsiloxanes (number-average molecular weight 1500, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 3.5%), 0.08g dibenzoyl peroxide
(BPO), 5g hexabromocyclododecane 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 40min 50
DEG C water bath with thermostatic control in polymerize 16 hours, it is then successively distinguished in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control to polymerase 17 h
Afterwards, it after product being washed, is scattered in 100g water, obtains galapectite support dispersion；10g lauryl sodium sulfate is taken to be added
In 100g water, sonic oscillation for 24 hours after, the carbon nanotube of 1g is added, ultrasonic disperse 10h obtains dispersion liquid；Above-mentioned dispersion liquid is taken out
1h is kept after vacuum, is then restored to normal pressure, is repeated vacuum step three times, is obtained carbon nanotube carrier wet gel；By 1g angstroms
Lip river stone support dispersion is mixed with 8g carbon nanotube carrier wet gel, is added 0.2g dibenzoyl peroxide (BPO), and 2g bis-phenol is double
(diphenyl phosphate), re-ultrasonic dispersion 1h are placed under 75 DEG C of water bath condition after prepolymerization 45min in 50 DEG C of water bath with thermostatic control
Polymerization 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, product is freezed dry
Dry, cryogenic temperature is -40 DEG C, and dry humidity is 30 DEG C, and dry vacuum degree is generally 4000pa, and it is small that drying time is generally 10
When, obtain the multiple dimensioned carrier aeroge of carbon nanotube/galapectite.
Embodiment 4
8g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 8g sodium styrene sulfonate, (number-average molecular weight 2000, contents of ethylene rubs the poly- divinylsiloxanes of 1g
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of your percentage 3%), 0.1g azodiisobutyronitrile (ABIN), 2g six
Bromine cyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 40min, is added to galapectite dispersion liquid
In, ultrasonic disperse 33min keeps 1h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, repeats vacuum step three times
Afterwards, it after product being washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 60min in 50 DEG C of constant temperature
It polymerize 24 hours in water-bath, after it is successively then polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, by product
It after washing, is scattered in 100g water, obtains galapectite support dispersion；It takes 8g lauryl sodium sulfate to be added in 100g water, surpasses
After sound oscillation 30h, the carbon nanotube of 6g is added, ultrasonic disperse for 24 hours, obtains dispersion liquid；It is kept after above-mentioned dispersion liquid is vacuumized
1h is then restored to normal pressure, repeats vacuum step three times, obtains carbon nanotube carrier wet gel；By 6g galapectite carrier point
Dispersion liquid is mixed with 20g carbon nanotube carrier wet gel, is added 0.8g azodiisobutyronitrile (ABIN), bis- (the phosphoric acid hexichol of 3g bis-phenol
Ester), it is small to be placed under 75 DEG C of water bath condition after prepolymerization 60min the polymerization 16 in 50 DEG C of water bath with thermostatic control by re-ultrasonic dispersion 4h
When, after it is successively then polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, product is freeze-dried, is freezed
Temperature is -80 DEG C, and dry humidity is 40 DEG C, and dry vacuum degree is generally 1000pa, and drying time is generally 20 hours, obtains carbon
The multiple dimensioned carrier aeroge of nanotube/galapectite.
Embodiment 5
9g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 10g sodium styrene sulfonate, 0.7g poly- divinylsiloxanes (number-average molecular weight 3000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of mole percent 2.5%), 0.06g dibenzoyl peroxide
(BPO), 1g hexabromocyclododecane 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 45min
It polymerize in 50 DEG C of water bath with thermostatic control 18 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；6g lauryl sodium sulfate is taken to be added
In 100g water, after sonic oscillation 35h, the carbon nanotube of 8g is added, ultrasonic disperse 20h obtains dispersion liquid；Above-mentioned dispersion liquid is taken out
1h is kept after vacuum, is then restored to normal pressure, is repeated vacuum step three times, is obtained carbon nanotube carrier wet gel；By 8g angstroms
Lip river stone support dispersion is mixed with 12g carbon nanotube carrier wet gel, is added 1g dibenzoyl peroxide (BPO), and 4g bis-phenol is double
(diphenyl phosphate), re-ultrasonic dispersion 6h are placed under 75 DEG C of water bath condition after prepolymerization 50min in 50 DEG C of water bath with thermostatic control
Polymerization 20 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, product is freezed dry
Dry, cryogenic temperature is -60 DEG C, and dry humidity is 50 DEG C, and dry vacuum degree is generally 50000pa, and it is small that drying time is generally 30
When, obtain the multiple dimensioned carrier aeroge of carbon nanotube/galapectite.
Embodiment 6
10g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 7g sodium styrene sulfonate, 0.9g poly- divinylsiloxanes (number-average molecular weight 1000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 4.5%), 0.07g azodiisobutyronitrile (ABIN),
0.1g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 20min, is added to galapectite point
In dispersion liquid, ultrasonic disperse 26min keeps 1h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats vacuum step
It after three times, after product is washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 50min at 50 DEG C
It polymerize 20 hours in water bath with thermostatic control, it, will after it is successively then polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After product washing, it is scattered in 100g water, obtains galapectite support dispersion；Take 5g lauryl sodium sulfate that 100g water is added
In, after sonic oscillation 40h, the carbon nanotube of 5g is added, ultrasonic disperse 15h obtains dispersion liquid；After above-mentioned dispersion liquid is vacuumized
1h is kept, normal pressure is then restored to, vacuum step is repeated three times, obtains carbon nanotube carrier wet gel；10g galapectite is carried
Dispersion liquid is mixed with 16g carbon nanotube carrier wet gel, is added 0.6g azodiisobutyronitrile (ABIN), the bis- (phosphoric acid of 5g bis-phenol
Diphenyl ester), re-ultrasonic dispersion 8h is placed under 75 DEG C of water bath condition and polymerize in 50 DEG C of water bath with thermostatic control after prepolymerization 55min
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, product is freeze-dried,
Cryogenic temperature is -95 DEG C, and dry humidity is 60 DEG C, and dry vacuum degree is generally 3000pa, and drying time is generally 40 hours, obtains
To the multiple dimensioned carrier aeroge of carbon nanotube/galapectite.
Embodiment 7
12g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 12g sodium styrene sulfonate, 1.6g poly- divinylsiloxanes (number-average molecular weight 500, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 5%), 0.3g dibenzoyl peroxide (BPO), 8g
Hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 60min, is added to galapectite dispersion liquid
In, ultrasonic disperse 34min keeps 0.5h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, repeats vacuum step three
It after secondary, after product is washed, is scattered in 100g water, is placed under 80 DEG C of water bath condition after prepolymerization 40min in 60 DEG C of perseverance
It polymerize in tepidarium 16 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, will produces
After object washing, it is scattered in 100g water, obtains galapectite support dispersion；12g lauryl sodium sulfate is taken to be added in 100g water,
Sonic oscillation for 24 hours after, the carbon nanotube of 12g is added, ultrasonic disperse 10h obtains dispersion liquid；It is protected after above-mentioned dispersion liquid is vacuumized
1h is held, normal pressure is then restored to, vacuum step is repeated three times, obtains carbon nanotube carrier wet gel；By 12g galapectite carrier
Dispersion liquid is mixed with 22g carbon nanotube carrier wet gel, is added 1.2g dibenzoyl peroxide (BPO), the bis- (di(2-ethylhexyl)phosphates of 7g bis-phenol
Phenyl ester), re-ultrasonic dispersion 1h is placed under 80 DEG C of water bath condition and polymerize 18 in 60 DEG C of water bath with thermostatic control after prepolymerization 45min
Hour, after it is successively then polymerize 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, product is freeze-dried, it is cold
Freezing temperature is -40 DEG C, and dry humidity is 30 DEG C, and dry vacuum degree is generally 4000pa, and drying time is generally 10 hours, obtains
The multiple dimensioned carrier aeroge of carbon nanotube/galapectite.
Embodiment 8
0.7g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
To galapectite dispersion liquid, by 0.7g sodium styrene sulfonate, 0.06g poly- divinylsiloxanes (number-average molecular weight 5000, vinyl
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of content mole percent 0.1%), 0.01g azodiisobutyronitrile
(ABIN), 0.08g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 40min, is added to
In galapectite dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats to take out
Vacuum step three times after, after product is washed, be scattered in 100g water, be placed under 70 DEG C of water bath condition after prepolymerization 60min
It polymerize in 40 DEG C of water bath with thermostatic control 24 hours, then successively gathers it respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After closing 8h, after product is washed, it is scattered in 100g water, obtains galapectite support dispersion；Take 0.6g lauryl sodium sulfate
It is added in 100g water, after sonic oscillation 30h, the carbon nanotube of 0.6g is added, ultrasonic disperse for 24 hours, obtains dispersion liquid；By above-mentioned point
Dispersion liquid keeps 1h after vacuumizing, be then restored to normal pressure, repeats vacuum step three times, obtains carbon nanotube carrier wet gel；
0.8g galapectite support dispersion is mixed with 0.7g carbon nanotube carrier wet gel, 0.01g azodiisobutyronitrile is added
(ABIN), 0.03g bis-phenol is bis- (diphenyl phosphate), re-ultrasonic dispersion 4h, is placed under 70 DEG C of water bath condition after prepolymerization 60min
It polymerize in 40 DEG C of water bath with thermostatic control 16 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, product is freeze-dried, cryogenic temperature is -80 DEG C, and dry humidity is 40 DEG C, and dry vacuum degree is generally 1000pa,
Drying time is generally 20 hours, obtains the multiple dimensioned carrier aeroge of carbon nanotube/galapectite.
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.
1 flame retardant property 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. fire-retardant carbon nanotube-galapectite aerogel composite, it is characterised in that: carbon nanotube-galapectite composite aerogel
Material average specific surface area is 604-609m2g-1, nanoscale is existed simultaneously in carbon nanotube-galapectite aerogel composite
With micro-meter scale hole, nanoscale hole average out to 10-12nm, 15-18 μm of average out to of micro-meter scale hole, according to following steps
It is rapid to carry out:
Step 1,0.7-12 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 0.7-12 parts by weight of styrene sodium sulfonate, 0.06-1.6 weight
The poly- divinylsiloxanes of part, 0.01-0.3 parts by weight initiator, 0.08-8 parts by weight hexabromocyclododecane 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, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization reaction time at least 50h is washed
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 percent
(i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-5%'s
The poly dimethyl divinylsiloxanes of amino list sealing end or the poly dimethyl divinylsiloxanes of amino bi-end-blocking；
Step 2, it takes 0.6-12 parts by weight lauryl sodium sulfate to be added in 100 parts by weight water, after sonic oscillation, is added thereto
The carbon nanotube of 0.6-12 parts by weight after ultrasonic disperse is uniform, keeps vacuum after vacuumizing, be then restored to normal pressure, repeats to take out
Vacuum step three times, obtains the wet gel of step 2；
Step 3, the dispersion liquid of 0.8-12 parts by weight step 1 is mixed with the wet gel of 0.7-22 parts by weight step 2, thereto plus
Entering 0.01-1.2 parts by weight initiator, 0.03-7 parts by weight of bisphenol is bis- (diphenyl phosphate), after ultrasonic disperse is uniform, warming-in-water
Initiated polymerization to 70-80 DEG C after polymerization reaction time at least 50h, product is freeze-dried, drying time at least 2h,
Obtain carbon nanotube-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 hexabromocyclododecane entered is also dispersed in halloysite nanotubes hollow structure, Ai Luo
Stone nanotube hollow structure provides microcellular structure for fire-retardant carbon nanotube-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
Hexabromocyclododecane is supported in halloysite nanotubes by structure, and step 3 to be located at poly- outside halloysite nanotubes hollow structure
Polymerize under the action of initiator between vinyl functional group in divinylsiloxanes so that halloysite nanotubes and
Tridimensional network is collectively formed in poly- divinylsiloxanes, and the carbon nanotube being added in step 2 is successfully configured to network pore
Structure, above-mentioned tridimensional network and carbon nanotube are successfully configured to network pore structure and together form three-dimensional network hole knot
Structure, above-mentioned three-dimensional network pore structure provide meso-hole structure for fire-retardant carbon nanotube-galapectite aerogel composite, simultaneously will
Bis-phenol bis- (diphenyl phosphates) is supported in meso-hole structure.
2. fire-retardant carbon nanotube-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 hexabromo
Cyclododecane is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added to galapectite dispersion liquid after stirring 10-60min
In, ultrasonic disperse 25-35min keeps vacuum 0.5-1.5h after vacuumizing, when carrying out polymerization reaction, selection is at 70-80 DEG C
It polymerize 12-24h under water bath condition after prepolymerization 30-60min in 40-60 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C,
90 DEG C, it polymerize 2-8h respectively in 100 DEG C of water bath with thermostatic control.
3. fire-retardant carbon nanotube-galapectite aerogel composite according to claim 1, it is characterised in that: in step 2
In, 1-10 parts by weight lauryl sodium sulfate is added to the water, after sonic oscillation 2-48h, 1-10 parts by weight are added thereto
Carbon nanotube after the uniform 1-24h of ultrasonic disperse, keeps vacuum 1h after vacuumizing.
4. fire-retardant carbon nanotube-galapectite aerogel composite according to claim 1, it is characterised in that: in step 3
In, the dispersion liquid of 1-10 parts by weight step 1 is mixed with the wet gel of 1-20 parts by weight step 2,0.01-1 weight is added thereto
Part initiator is measured, 0.05-5 parts by weight of bisphenol is bis- (diphenyl phosphate), after ultrasonic disperse is uniform, the selection when carrying out polymerization reaction
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, freeze-drying condition is -6 DEG C of temperature -- 105 DEG C,
2-55 DEG C of humidity, vacuum degree 10-50000pa, time 2-48h.
5. fire-retardant carbon nanotube-galapectite aerogel composite according to claim 1, it is characterised in that: initiator
Select dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
6. fire-retardant carbon nanotube-galapectite aerogel composite preparation method, it is characterised in that: as steps described below into
Row:
Step 1,0.7-12 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 0.7-12 parts by weight of styrene sodium sulfonate, 0.06-1.6 weight
The poly- divinylsiloxanes of part, 0.01-0.3 parts by weight initiator, 0.08-8 parts by weight hexabromocyclododecane 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, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization reaction time at least 50h is washed
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 percent
(i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-5%'s
The poly dimethyl divinylsiloxanes of amino list sealing end or the poly dimethyl divinylsiloxanes of amino bi-end-blocking；
Step 2, it takes 0.6-12 parts by weight lauryl sodium sulfate to be added in 100 parts by weight water, after sonic oscillation, is added thereto
The carbon nanotube of 0.6-12 parts by weight after ultrasonic disperse is uniform, keeps vacuum after vacuumizing, be then restored to normal pressure, repeats to take out
Vacuum step three times, obtains the wet gel of step 2；
Step 3, the dispersion liquid of 0.8-12 parts by weight step 1 is mixed with the wet gel of 0.7-22 parts by weight step 2, thereto plus
Entering 0.01-1.2 parts by weight initiator, 0.03-7 parts by weight of bisphenol is bis- (diphenyl phosphate), after ultrasonic disperse is uniform, warming-in-water
Initiated polymerization to 70-80 DEG C after polymerization reaction time at least 50h, product is freeze-dried, drying time at least 2h,
Obtain carbon nanotube-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 hexabromocyclododecane entered is also dispersed in halloysite nanotubes hollow structure, Ai Luo
Stone nanotube hollow structure provides microcellular structure for fire-retardant carbon nanotube-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
Hexabromocyclododecane is supported in halloysite nanotubes by structure, and step 3 to be located at poly- outside halloysite nanotubes hollow structure
Polymerize under the action of initiator between vinyl functional group in divinylsiloxanes so that halloysite nanotubes and
Tridimensional network is collectively formed in poly- divinylsiloxanes, and the carbon nanotube being added in step 2 is successfully configured to network pore
Structure, above-mentioned tridimensional network and carbon nanotube are successfully configured to network pore structure and together form three-dimensional network hole knot
Structure, above-mentioned three-dimensional network pore structure provide meso-hole structure for fire-retardant carbon nanotube-galapectite aerogel composite, simultaneously will
Bis-phenol bis- (diphenyl phosphates) is supported in meso-hole structure.
7. the preparation method of fire-retardant carbon nanotube-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 hexabromocyclododecane is added in the mixed solution of water and ethyl alcohol, is added to above-mentioned solution angstrom after stirring 10-60min
In the stone dispersion liquid of Lip river, ultrasonic disperse 25-35min keeps vacuum 0.5-1.5h after vacuumizing, when carrying out polymerization reaction, selection exists
Polymerize 12-24h under 70-80 DEG C of water bath condition after prepolymerization 30-60min in 40-60 DEG C of water bath with thermostatic control, then by its according to
It is secondary to 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 fire-retardant carbon nanotube-galapectite aerogel composite according to claim 6, feature exist
In: in step 2,1-10 parts by weight lauryl sodium sulfate is added to the water, after sonic oscillation 2-48h, 1- is added thereto
The carbon nanotube of 10 parts by weight after the uniform 1-24h of ultrasonic disperse, keeps vacuum 1h after vacuumizing.
9. the preparation method of fire-retardant carbon nanotube-galapectite aerogel composite according to claim 6, feature exist
In: in step 3, the dispersion liquid of 1-10 parts by weight step 1 is mixed with the wet gel of 1-20 parts by weight step 2, thereto plus
Enter 0.01-1 parts by weight initiator, 0.05-5 parts by weight of bisphenol is bis- (diphenyl phosphate), after ultrasonic disperse is uniform, 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 then successively polymerize to 2-8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, freeze-drying condition is temperature-
6 DEG C -- 105 DEG C, 2-55 DEG C of humidity, vacuum degree 10-50000pa, time 2-48h.
10. the preparation method of fire-retardant carbon nanotube-galapectite aerogel composite according to claim 6, feature
Be: initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
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