CN109081354A - Fire-retardant galapectite-silicon dioxide composite aerogel material and preparation method thereof - Google Patents
Fire-retardant galapectite-silicon dioxide composite aerogel material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides fire-retardant galapectite-silicon dioxide composite aerogel material and preparation method thereof, after galapectite dispersion liquid is polymerize with the mixed solution of hexabromocyclododecane, after ethyl orthosilicate, hydrochloric acid, bis-phenol bis- (diphenyl phosphates) and initiator are added into polymerizate again, polymerization reaction is carried out again, sodium hydroxide is added in reaction process, and the reaction was continued, obtains fire-retardant galapectite-silicon dioxide composite aerogel material.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 galapectite-silica
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, the village full the name of super galapectite, structure, pattern and curling mechanism
[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 galapectite-silicon dioxide 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 galapectite-silicon dioxide composite aerogel material and preparation method thereof carries out as steps described below:
Step 1,0.6-16 parts by weight halloysite nanotubes are added to 50 parts by weight of deionized water and 50 parts by weight of ethanol
Mixed liquor in, ultrasonic disperse is uniform, obtain galapectite dispersion liquid, by 0.6-16 parts by weight of styrene sodium sulfonate, 0.06-4 weight
The poly- divinylsiloxanes of part, 0.01-0.4 parts by weight initiator are measured, 0.05-12 parts by weight hexabromocyclododecane is added to 50 weights
In the mixed liquor for measuring part deionized water and 50 parts by weight of ethanol, above-mentioned solution is added to galapectite dispersion liquid after mixing evenly
In, ultrasonic disperse is uniform, and vacuum is kept after vacuumizing, and is then restored to normal pressure, and after repeating vacuum step three times, product is washed
It washs, is then dispersed in 100 parts by weight water, warming-in-water to 60-120 DEG C of initiated polymerization, polymerization reaction time is at least
48h obtains the product of step 1；
Step 2, it is scattered in 100 parts by weight water after the product of step 1 being washed, the positive silicic acid second of 74-154 parts by weight is added
Ester, 0.07-1.5 parts by weight 12mol/L hydrochloric acid, the bis- (phosphoric acid of the bis-phenol of 0.01-1.8 parts by weight initiator and 0.08-16 parts by weight
Diphenyl ester), after mixing evenly, 0.01-0.4 parts by weight hydrogen-oxygen is then added in warming-in-water to initiated polymerization at 30-75 DEG C
Change sodium, stirring is completely dissolved to it, and polymerization reaction time is at least 48h, and it is compound wet solidifying to obtain fire-retardant galapectite-silica
Glue；
Step 3,0.08-1.2 parts by weight methacryloxypropyl is added in the fire-retardant compound wet gel of galapectite-silica
Base dodecyl trimethyl ammonium chloride, after standing, place the product in CO2In supercritical high-pressure extraction device, with CO2Exist for medium
Supercritical drying at least 1h is carried out under 32-58 DEG C of temperature and air pressure 6-12MPa, it is multiple that fire-retardant galapectite-silica can be obtained
Close aerogel material.
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.
In step 1, halloysite nanotubes are 1-15 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol ultrasonic
Disperse 1-2h, sodium styrene sulfonate is 1-15 parts by weight, and poly- divinylsiloxanes are 0.1-2 parts by weight, initiator 0.01-
0.1 parts by weight, hexabromocyclododecane are 0.1-10 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol and stir 15-
It after 65min, is added in galapectite dispersion liquid, ultrasonic disperse 20-40min keeps 1-2h after vacuumizing above-mentioned mixed liquor.
In step 1, when carrying out polymerization reaction, selection polymerize 10-60min at 60-120 DEG C, is then cooled to 15-
It polymerize 12-24h at 50 DEG C, then successively polymerize 2-8h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
In step 2,80-150 parts by weight ethyl orthosilicate, 0.1-1 parts by weight 12mol/L are added into above-mentioned dispersion liquid
Hydrochloric acid, 0.01-1 parts by weight initiator and 0.1-15 parts by weight of bisphenol bis- (diphenyl phosphates) stir 10-70min.
Initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
In step 2, when carrying out polymerization reaction, selection polymerize 10-40min at 30-75 DEG C, and 0.01-0.2 weight is added
Part sodium hydroxide is measured, stirring is completely dissolved to it, is then cooled in 20-50 DEG C of water bath with thermostatic control and polymerize 20-35h, then successively
It polymerize 2-4h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
In step 3, methacryloxy dodecyl trimethyl ammonium chloride is 0.1-1 parts by weight, and time of repose is
1-6h, the condition of supercritical drying are that supercritical drying 2-4h, preferably 3h are carried out at 33-50 DEG C of temperature and air pressure 7-10MPa.
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 galapectite-silicon dioxide composite aerogel material, 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 2 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, the ethyl orthosilicate being added in step 2, hydrochloric acid and hydroxide is collectively formed in pipe and poly- divinylsiloxanes
Sodium reacts to form SiO2Particle, SiO2Particle is configured to network pore structure, above-mentioned tridimensional network and SiO2Particle structure
Network pore structure made of building together forms three-dimensional network pore structure, and above-mentioned three-dimensional network pore structure is fire-retardant angstrom of Lip river
Stone-silicon dioxide composite aerogel material provides meso-hole structure, while bis-phenol bis- (diphenyl phosphates) 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 attached drawing 1.It can from figure
To 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
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, it can be with
Sample interior is found out there are more micropore, is as caused by absorption potential strong inside micropore.By nitrogen adsorption desorption isotherm number
According to the sample specific surface area can reach 602.14m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, through more
The average specific surface area of group measurement material is 600-604m2g-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=-0.963/ln (p/p0), unit nm, while adding adsorbent layer thickness
T=0.349 [- 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 10.26nm, and another kind is 20.32 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.
It is saturating using the Nanosem430 field emission scanning electron microscope and Tecnai G2F20 Flied emission of Dutch Philips
It penetrates electron microscope to observe the microscopic appearance of the composite material prepared using the method for the invention, as shown in Figure 2.From
As can be seen that SiO in figure2Particle is successfully configured to network pore structure, and aperture size is in mesoporous scale.It is overlapped to form three-dimensional netted
Halloysite nanotubes be uniformly dispersed in SiO2In three-dimensional network hole, the building of dual load system is realized.
Detailed description of the invention
Fig. 1 is fire-retardant galapectite-silicon dioxide composite aerogel material N2Adsorption-desorption curve；
Fig. 2 is fire-retardant galapectite-silicon dioxide composite aerogel material electromicroscopic photograph.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1.
1 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 6 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.4 parts by weight
(number-average molecular weight 1000, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 4%),
0.01 parts by weight aoxidize dibenzoyl (BPO), and 10 parts by weight hexabromocyclododecane are added to 50 parts by weight of deionized water and 50 weights
In the mixed liquor for measuring part ethyl alcohol, 15min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 20min, by above-mentioned mixed liquor
1h is kept after vacuumizing, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 weights are then dispersed in
It measures in part water, is placed under 120 DEG C of water bath condition after prepolymerization 25min in 50 DEG C of water bath with thermostatic control and polymerize 12 hours, then
After it is successively polymerize 4h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 parts by weight are scattered in after product is washed
In water, 88 parts by weight ethyl orthosilicates, 0.9 parts by weight 12mol/L hydrochloric acid are added, 1 parts by weight aoxidize dibenzoyl (BPO) and 6
The bis-phenol of parts by weight is bis- (diphenyl phosphate), at room temperature stir 10min after under 65 DEG C of water bath condition prepolymerization 10min, with
After be added 0.01 parts by weight of sodium hydroxide, stirring is completely dissolved to it, then polymerize 25 hours in 40 DEG C of water bath with thermostatic control, with
It is successively respectively placed in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control to obtain fire-retardant galapectite-silica after 2h compound afterwards
0.4 parts by weight methacryloxy dodecyl trimethyl ammonium chloride is added in wet gel in wet gel, will after standing 1h
Product is placed in CO2In supercritical high-pressure extraction device, with CO2Supercritical drying is carried out under temperature 50 C and air pressure 7MPa for medium
Fire-retardant galapectite-silicon dioxide composite aerogel material can be obtained in dry 3h.
Embodiment 2.
15 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 2h obtains galapectite dispersion liquid, by 10 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.1 parts by weight
(number-average molecular weight 3000, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 2%),
0.1 parts by weight azodiisobutyronitrile (ABIN), 5 parts by weight hexabromocyclododecane are added to 50 parts by weight of deionized water and 50 weight
In the mixed liquor of part ethyl alcohol, 62min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 40min takes out above-mentioned mixed liquor
2h is kept after vacuum, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 weight are then dispersed in
In part water, it is placed under 98 DEG C of water bath condition after prepolymerization 43min and polymerize 19 hours in 40 DEG C of water bath with thermostatic control, then by it
After successively polymerizeing 8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 parts by weight water are scattered in after product is washed
In, be added 80 parts by weight ethyl orthosilicates, 0.5 parts by weight 12mol/L hydrochloric acid, 0.5 parts by weight azodiisobutyronitrile (ABIN) and
The bis-phenol of 15 parts by weight is bis- (diphenyl phosphate), at room temperature stir 70min after under 55 DEG C of water bath condition prepolymerization 40min,
0.13 parts by weight of sodium hydroxide is then added, stirring is completely dissolved to it, then polymerize 20 hours in 50 DEG C of water bath with thermostatic control,
It is then successively respectively placed in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control to obtain fire-retardant galapectite-silica after 4h multiple
Wet gel is closed, 0.2 parts by weight methacryloxy dodecyl trimethyl ammonium chloride is added in wet gel, after standing 6h,
Place the product in CO2In supercritical high-pressure extraction device, with CO2It is carried out under temperature 45 C and air pressure 8MPa for medium overcritical
Dry 3h, can be obtained fire-retardant galapectite-silicon dioxide composite aerogel material.
Embodiment 3.
8 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1.5h obtains galapectite dispersion liquid, by 15 parts by weight of styrene sodium sulfonates, the poly- divinyl silicon oxygen of 0.8 parts by weight
Alkane (number-average molecular weight 2000, the poly dimethyl divinyl silicon oxygen of the amino bi-end-blocking of contents of ethylene mole percent 3%
Alkane), 0.08 parts by weight azodiisobutyronitrile (ABIN), 3 parts by weight hexabromocyclododecane be added to 50 parts by weight of deionized water and
In the mixed liquor of 50 parts by weight of ethanol, 52min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, it will be above-mentioned mixed
It closes after liquid vacuumizes and keeps 1.5h, be then restored to normal pressure, after repeating vacuum step three times, product is washed, is then dispersed
In 100 parts by weight water, it is small that in 30 DEG C of water bath with thermostatic control polymerization 18 is placed under 60 DEG C of water bath condition after prepolymerization 10min
When, after it is successively then polymerize 5h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, it is scattered in after product is washed
In 100 parts by weight water, 150 parts by weight ethyl orthosilicates are added, 0.1 parts by weight 12mol/L hydrochloric acid, 0.9 parts by weight azo two is different
Butyronitrile (ABIN) and the bis-phenol of 4 parts by weight are bis- (diphenyl phosphate), pre- under 66 DEG C of water bath condition after stirring 30min at room temperature
It polymerize 20min, 0.19 parts by weight of sodium hydroxide is then added, stirs to it and be completely dissolved, then in 30 DEG C of water bath with thermostatic control
Polyase 13 0 hour, fire-retardant galapectite-was obtained after it is successively respectively then placed 3h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
1 parts by weight methacryloxy dodecyl trimethyl ammonium chloride is added in the compound wet gel of silica in wet gel, quiet
After setting 2h, place the product in CO2In supercritical high-pressure extraction device, with CO2For medium at 38 DEG C of temperature and air pressure 8.5MPa into
Fire-retardant galapectite-silicon dioxide composite aerogel material can be obtained in row supercritical drying 2.5h.
Embodiment 4.
3 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 5 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.9 parts by weight
(number-average molecular weight 4000, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 1%),
0.04 parts by weight aoxidize dibenzoyl (BPO), and 8 parts by weight hexabromocyclododecane are added to 50 parts by weight of deionized water and 50 weight
In the mixed liquor of part ethyl alcohol, 60min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min takes out above-mentioned mixed liquor
1h is kept after vacuum, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 weight are then dispersed in
In part water, it is placed under 85 DEG C of water bath condition after prepolymerization 19min and polymerize 15 hours in 25 DEG C of water bath with thermostatic control, then by it
After successively distinguishing polyase 13 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 parts by weight water are scattered in after product is washed
In, 90 parts by weight ethyl orthosilicates, 1 parts by weight 12mol/L hydrochloric acid are added, 0.3 parts by weight aoxidize dibenzoyl (BPO) and 7 weights
Measure part bis-phenol it is bis- (diphenyl phosphate), at room temperature stirring 55min after under 75 DEG C of water bath condition prepolymerization 15min, then
It is added 0.02 parts by weight of sodium hydroxide, stirring is completely dissolved to it, then polymerize 28 hours in 45 DEG C of water bath with thermostatic control, then
It is successively respectively placed in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control to obtain fire-retardant galapectite-silica after 2h compound wet
0.7 parts by weight methacryloxy dodecyl trimethyl ammonium chloride is added in gel in wet gel, after standing 3h, will produce
Object is placed in CO2In supercritical high-pressure extraction device, with CO2Supercritical drying is carried out at 43 DEG C of temperature and air pressure 7.5MPa for medium
Fire-retardant galapectite-silicon dioxide composite aerogel material can be obtained in dry 3h.
Embodiment 5.
4 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 3 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 1.4 parts by weight
(number-average molecular weight 5000, the poly dimethyl divinyl silicon oxygen of the amino bi-end-blocking of contents of ethylene mole percent 0.1%
Alkane), 0.05 parts by weight aoxidize dibenzoyl (BPO), 0.1 parts by weight hexabromocyclododecane be added to 50 parts by weight of deionized water and
In the mixed liquor of 50 parts by weight of ethanol, 35min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, it will be above-mentioned mixed
It closes after liquid vacuumizes and keeps 1h, be then restored to normal pressure, after repeating vacuum step three times, product is washed, is then dispersed in
In 100 parts by weight water, it is placed under 110 DEG C of water bath condition after prepolymerization 31min and polymerize 24 hours in 35 DEG C of water bath with thermostatic control,
After it is successively then polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 weights are scattered in after product is washed
It measures in part water, 89 parts by weight ethyl orthosilicates, 0.7 parts by weight 12mol/L hydrochloric acid is added, 0.1 parts by weight aoxidize dibenzoyl
(BPO) and the bis-phenol of 0.1 parts by weight is bis- (diphenyl phosphate), stirs the pre-polymerization under 44 DEG C of water bath condition after 41min at room temperature
33min is closed, 0.2 parts by weight of sodium hydroxide is then added, stirring is completely dissolved to it, then polymerize in 20 DEG C of water bath with thermostatic control
26 hours, fire-retardant galapectite-dioxy was obtained after it is successively respectively then placed 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
0.8 parts by weight methacryloxy dodecyl trimethyl ammonium chloride is added in the compound wet gel of SiClx in wet gel, stands
After 6h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is carried out at 33 DEG C of temperature and air pressure 10MPa for medium
Fire-retardant galapectite-silicon dioxide composite aerogel material can be obtained in supercritical drying 3.5h.
Embodiment 6.
9 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 1 parts by weight of styrene sodium sulfonate, the poly- divinylsiloxanes of 1.8 parts by weight
(number-average molecular weight 500, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 5%),
0.07 parts by weight azodiisobutyronitrile (ABIN), 4 parts by weight hexabromocyclododecane are added to 50 parts by weight of deionized water and 50 weights
In the mixed liquor for measuring part ethyl alcohol, 44min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, by above-mentioned mixed liquor
1h is kept after vacuumizing, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 weights are then dispersed in
It measures in part water, is placed under 80 DEG C of water bath condition after prepolymerization 60min and polymerize 20 hours in 15 DEG C of water bath with thermostatic control, then will
After it successively polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 parts by weight water are scattered in after product is washed
In, 87 parts by weight ethyl orthosilicates, 0.8 parts by weight 12mol/L hydrochloric acid, 0.8 parts by weight azodiisobutyronitrile (ABIN) and 5 is added
The bis-phenol of parts by weight is bis- (diphenyl phosphate), at room temperature stir 60min after under 30 DEG C of water bath condition prepolymerization 25min, with
After be added 0.18 parts by weight of sodium hydroxide, stirring is completely dissolved to it, then polyase 13 5 hours in 35 DEG C of water bath with thermostatic control, with
It is successively respectively placed in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control to obtain fire-retardant galapectite-silica after 2h compound afterwards
0.1 parts by weight methacryloxy dodecyl trimethyl ammonium chloride is added in wet gel in wet gel, after standing 3.5h,
Place the product in CO2In supercritical high-pressure extraction device, with CO2It is carried out at 39 DEG C of temperature and air pressure 9MPa for medium overcritical
Dry 3h, can be obtained fire-retardant galapectite-silicon dioxide composite aerogel material.
Embodiment 7
16 parts by weight halloysite nanotubes are added in the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol,
Ultrasonic disperse 1h obtains galapectite dispersion liquid, by 16 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 4 parts by weight (number
Average molecular weight 2500, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 1.5%),
0.4 parts by weight azodiisobutyronitrile (ABIN), 12 parts by weight hexabromocyclododecane are added to 50 parts by weight of deionized water and 50 weights
In the mixed liquor for measuring part ethyl alcohol, 55min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, by above-mentioned mixed liquor
1h is kept after vacuumizing, is then restored to normal pressure, after repeating vacuum step three times, product is washed, 100 weights are then dispersed in
It measures in part water, is placed under 120 DEG C of water bath condition after prepolymerization 25min in 50 DEG C of water bath with thermostatic control and polymerize 12 hours, then
After it is successively polymerize 4h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, 100 parts by weight are scattered in after product is washed
In water, 154 parts by weight ethyl orthosilicates, 1.5 parts by weight 12mol/L hydrochloric acid, 1.8 parts by weight azodiisobutyronitriles (ABIN) are added
It is bis- (diphenyl phosphate) with the bis-phenol of 16 parts by weight, the prepolymerization under 65 DEG C of water bath condition after 45min is stirred at room temperature
0.4 parts by weight of sodium hydroxide is then added in 40min, and stirring is completely dissolved to it, then polymerize 25 in 40 DEG C of water bath with thermostatic control
Hour, fire-retardant galapectite-titanium dioxide is obtained after it is successively respectively then placed 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
1.2 parts by weight methacryloxy dodecyl trimethyl ammonium chloride are added in the compound wet gel of silicon in wet gel, stand 3h
Afterwards, place the product in CO2In supercritical high-pressure extraction device, with CO2Super face is carried out at 32 DEG C of temperature and air pressure 6MPa for medium
4h is dried on boundary, and fire-retardant galapectite-silicon dioxide composite aerogel material can be obtained.
Embodiment 8
0.6 parts by weight halloysite nanotubes are added to the mixed liquor of 50 parts by weight of deionized water and 50 parts by weight of ethanol
In, ultrasonic disperse 1h obtains galapectite dispersion liquid, by 0.6 parts by weight of styrene sodium sulfonate, the poly- divinyl silicon of 0.06 parts by weight
Oxygen alkane (number-average molecular weight 1500, the poly dimethyl divinyl silicon of the amino bi-end-blocking of contents of ethylene mole percent 0.8%
Oxygen alkane), 0.01 parts by weight aoxidize dibenzoyl (BPO), and 0.05 parts by weight hexabromocyclododecane is added to 50 parts by weight deionizations
In water and the mixed liquor of 50 parts by weight of ethanol, 60min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min will be upper
It states and keeps 1h after mixed liquor vacuumizes, be then restored to normal pressure, after repeating vacuum step three times, product is washed, is then divided
It dissipates in 100 parts by weight water, it is small to be placed under 85 DEG C of water bath condition after prepolymerization 19min the polymerization 15 in 25 DEG C of water bath with thermostatic control
When, 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 is scattered in after product is washed
In 100 parts by weight water, 74 parts by weight ethyl orthosilicates, 0.07 parts by weight 12mol/L hydrochloric acid are added, 0.01 parts by weight aoxidize hexichol
Formyl (BPO) and the bis-phenol of 0.08 parts by weight are bis- (diphenyl phosphate), at room temperature after stirring 55min under 75 DEG C of water bath condition
0.08 parts by weight of sodium hydroxide is then added in prepolymerization 15min, stirs to it and is completely dissolved, then in 45 DEG C of water bath with thermostatic control
Middle polymerization 28 hours, obtains fire-retardant angstrom of Lip river after it is successively respectively then placed 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
0.05 parts by weight methacryloxy trimethyl chlorine is added in the compound wet gel of stone-silica in wet gel
Change ammonium, after standing 2.5h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 58 DEG C of temperature and air pressure
Supercritical drying 2h is carried out under 12MPa, and fire-retardant galapectite-silicon dioxide composite aerogel material can be obtained.
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. fire-retardant galapectite-silicon dioxide composite aerogel material, it is characterised in that: galapectite-silicon dioxide composite aerogel
Material average specific surface area is 600-604m2g-1, nanoscale is existed simultaneously in galapectite-silicon dioxide composite aerogel material
With micro-meter scale hole, nanoscale hole average out to 10-11nm, 20-21 μm of average out to of micro-meter scale hole, according to following steps
It is rapid to carry out:
Step 1,0.6-16 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 0.6-16 parts by weight of styrene sodium sulfonate, 0.06-4 parts by weight
Poly- divinylsiloxanes, 0.01-0.4 parts by weight initiator, 0.05-12 parts by weight hexabromocyclododecane are added to 50 parts by weight
In the mixed liquor of deionized water and 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, is surpassed
Sound is uniformly dispersed, and vacuum is kept after vacuumizing, and is then restored to normal pressure, after repeating vacuum step three times, product is washed, so
After be scattered in 100 parts by weight water, warming-in-water to 60-120 DEG C of initiated polymerization, polymerization reaction time is at least 48h, obtains
To the product 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 is scattered in 100 parts by weight water after the product of step 1 being washed, 74-154 parts by weight ethyl orthosilicate is added,
0.07-1.5 parts by weight 12mol/L hydrochloric acid, the bis- (di(2-ethylhexyl)phosphates of the bis-phenol of 0.01-1.8 parts by weight initiator and 0.08-16 parts by weight
Phenyl ester), after mixing evenly, 0.01-0.4 parts by weight hydroxide is then added in warming-in-water to initiated polymerization at 30-75 DEG C
Sodium, stirring are completely dissolved to it, and polymerization reaction time is at least 48h, obtains the fire-retardant compound wet gel of galapectite-silica；
Step 3,0.08-1.2 parts by weight methacryloxy ten is added in the fire-retardant compound wet gel of galapectite-silica
Dialkyl group trimethyl ammonium chloride, after standing, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature
Supercritical drying at least 1h is carried out under 32-58 DEG C and air pressure 6-12MPa, and the fire-retardant compound gas of galapectite-silica can be obtained
Gel rubber material；
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 galapectite-silicon dioxide composite aerogel material, through vacuumizing,
After washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed inside halloysite nanotubes and are formed crosslinking knot
Hexabromocyclododecane is supported in halloysite nanotubes by structure, and step 2 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 ethyl orthosilicate being added in step 2, hydrochloric acid and sodium hydroxide are sent out
Raw reaction forms SiO2Particle, SiO2Particle is configured to network pore structure, above-mentioned tridimensional network and SiO2Particle building and
At network pore structure together form three-dimensional network pore structure, above-mentioned three-dimensional network pore structure is fire-retardant galapectite-
Silicon dioxide composite aerogel material provides meso-hole structure, while bis-phenol bis- (diphenyl phosphates) being supported in meso-hole structure.
2. fire-retardant galapectite-silicon dioxide composite aerogel material according to claim 1, it is characterised in that: in step 1
In, halloysite nanotubes are 1-15 parts by weight, are added to ultrasonic disperse 1-2h, styrene in the mixed liquor of deionized water and ethyl alcohol
Sodium sulfonate is 1-15 parts by weight, and poly- divinylsiloxanes are 0.1-2 parts by weight, and initiator is 0.01-0.1 parts by weight, hexabromo
Cyclododecane is 0.1-10 parts by weight, is added to after stirring 15-65min in the mixed liquor of deionized water and ethyl alcohol, is added to angstrom
In the stone dispersion liquid of Lip river, ultrasonic disperse 20-40min keeps 1-2h after vacuumizing above-mentioned mixed liquor, the choosing when carrying out polymerization reaction
Select and polymerize 10-60min at 60-120 DEG C, be then cooled at 15-50 DEG C and polymerize 12-24h, then successively at 80 DEG C, 90 DEG C and
It polymerize 2-8h respectively at 100 DEG C.
3. fire-retardant galapectite-silicon dioxide composite aerogel material according to claim 1, it is characterised in that: in step 2
In, 80-150 parts by weight ethyl orthosilicate, 0.1-1 parts by weight 12mol/L hydrochloric acid, 0.01-1 weight are added into above-mentioned dispersion liquid
Part initiator and 0.1-15 parts by weight of bisphenol bis- (diphenyl phosphates) stir 10-70min, and when carrying out polymerization reaction, selection exists
It polymerize 10-40min at 30-75 DEG C, 0.01-0.2 parts by weight of sodium hydroxide is added, stirring is completely dissolved to it, is then cooled to
It polymerize 20-35h in 20-50 DEG C of water bath with thermostatic control, then successively polymerize 2-4h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
4. fire-retardant galapectite-silicon dioxide composite aerogel material according to claim 1, it is characterised in that: initiator
Select dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
5. fire-retardant galapectite-silicon dioxide composite aerogel material according to claim 1, it is characterised in that: in step 3
In, methacryloxy dodecyl trimethyl ammonium chloride is 0.1-1 parts by weight, time of repose 1-6h, supercritical drying
Condition be that supercritical drying 2-4h, preferably 3h are carried out at 33-50 DEG C of temperature and air pressure 7-10MPa.
6. the method for preparing fire-retardant galapectite-silicon dioxide composite aerogel material as claimed in claim 1 to 5,
It is characterized in that: carrying out as steps described below:
Step 1,0.6-16 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 0.6-16 parts by weight of styrene sodium sulfonate, 0.06-4 parts by weight
Poly- divinylsiloxanes, 0.01-0.4 parts by weight initiator, 0.05-12 parts by weight hexabromocyclododecane are added to 50 parts by weight
In the mixed liquor of deionized water and 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, is surpassed
Sound is uniformly dispersed, and vacuum is kept after vacuumizing, and is then restored to normal pressure, after repeating vacuum step three times, product is washed, so
After be scattered in 100 parts by weight water, warming-in-water to 60-120 DEG C of initiated polymerization, polymerization reaction time is at least 48h, obtains
To the product 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 is scattered in 100 parts by weight water after the product of step 1 being washed, 74-154 parts by weight ethyl orthosilicate is added,
0.07-1.5 parts by weight 12mol/L hydrochloric acid, the bis- (di(2-ethylhexyl)phosphates of the bis-phenol of 0.01-1.8 parts by weight initiator and 0.08-16 parts by weight
Phenyl ester), after mixing evenly, 0.01-0.4 parts by weight hydroxide is then added in warming-in-water to initiated polymerization at 30-75 DEG C
Sodium, stirring are completely dissolved to it, and polymerization reaction time is at least 48h, obtains the fire-retardant compound wet gel of galapectite-silica；
Step 3,0.08-1.2 parts by weight methacryloxy ten is added in the fire-retardant compound wet gel of galapectite-silica
Dialkyl group trimethyl ammonium chloride, after standing, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature
Supercritical drying at least 1h is carried out under 32-58 DEG C and air pressure 6-12MPa, and the fire-retardant compound gas of galapectite-silica can be obtained
Gel rubber material；
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 galapectite-silicon dioxide composite aerogel material, through vacuumizing,
After washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed inside halloysite nanotubes and are formed crosslinking knot
Hexabromocyclododecane is supported in halloysite nanotubes by structure, and step 2 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 ethyl orthosilicate being added in step 2, hydrochloric acid and sodium hydroxide are sent out
Raw reaction forms SiO2Particle, SiO2Particle is configured to network pore structure, above-mentioned tridimensional network and SiO2Particle building and
At network pore structure together form three-dimensional network pore structure, above-mentioned three-dimensional network pore structure is fire-retardant galapectite-
Silicon dioxide composite aerogel material provides meso-hole structure, while bis-phenol bis- (diphenyl phosphates) being supported in meso-hole structure.
7. the preparation method of fire-retardant galapectite-silicon dioxide composite aerogel material according to claim 6, feature exist
In: in step 1, halloysite nanotubes are 1-15 parts by weight, are added to ultrasonic disperse in the mixed liquor of deionized water and ethyl alcohol
1-2h, sodium styrene sulfonate are 1-15 parts by weight, and poly- divinylsiloxanes are 0.1-2 parts by weight, initiator 0.01-0.1
Parts by weight, hexabromocyclododecane are 0.1-10 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol and stir 15-65min
Afterwards, it is added in galapectite dispersion liquid, ultrasonic disperse 20-40min keeps 1-2h after vacuumizing above-mentioned mixed liquor, is carrying out
Selection polymerize 10-60min at 60-120 DEG C when polymerization reaction, is then cooled at 15-50 DEG C and polymerize 12-24h, then successively exists
It polymerize 2-8h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
8. the preparation method of fire-retardant galapectite-silicon dioxide composite aerogel material according to claim 6, feature exist
In: in step 2, into above-mentioned dispersion liquid be added 80-150 parts by weight ethyl orthosilicate, 0.1-1 parts by weight 12mol/L hydrochloric acid,
0.01-1 parts by weight initiator and 0.1-15 parts by weight of bisphenol bis- (diphenyl phosphates) stir 10-70min, are carrying out polymerization reaction
When selection polymerize 10-40min at 30-75 DEG C, be added 0.01-0.2 parts by weight of sodium hydroxide, stirring is completely dissolved to it, so
It is cooled in 20-50 DEG C of water bath with thermostatic control afterwards and polymerize 20-35h, then successively polymerize 2-4h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
9. the preparation method of fire-retardant galapectite-silicon dioxide composite aerogel material according to claim 6, feature exist
In: initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
10. the preparation method of fire-retardant galapectite-silicon dioxide composite aerogel material according to claim 6, feature
Be: in step 3, methacryloxy dodecyl trimethyl ammonium chloride is 0.1-1 parts by weight, time of repose 1-
6h, the condition of supercritical drying are that supercritical drying 2-4h, preferably 3h are carried out at 33-50 DEG C of temperature and air pressure 7-10MPa.
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| CN115672263A (en) * | 2022-12-02 | 2023-02-03 | 东莞理工学院 | Preparation method of halloysite nanotube composite material and application of halloysite nanotube composite material in uranium pollution treatment |
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