CN109694539A - Fire-retardant galapectite-montmorillonite Composite aerogel material and preparation method thereof - Google Patents
Fire-retardant galapectite-montmorillonite Composite aerogel material and preparation method thereof Download PDFInfo
- Publication number
- CN109694539A CN109694539A CN201710986549.6A CN201710986549A CN109694539A CN 109694539 A CN109694539 A CN 109694539A CN 201710986549 A CN201710986549 A CN 201710986549A CN 109694539 A CN109694539 A CN 109694539A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- galapectite
- montmorillonite
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention provides fire-retardant galapectite-montmorillonite Composite aerogel material and preparation method thereof, galapectite dispersion liquid is obtained after galapectite dispersion liquid is polymerize with the mixed solution of hexabromocyclododecane, montmorillonite dispersions are prepared again, it is added after initiator that the reaction was continued after two kinds of dispersion liquids are mixed with bis-phenol bis- (diphenyl phosphates) thereto, obtains fire-retardant galapectite-montmorillonite 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, more specifically to a kind of fire-retardant galapectite-montmorillonite Composite gas
Gel rubber 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 galapectite-montmorillonite Composite airsetting glue material
Material and preparation method thereof, uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilize aeroge
Meso-hole structure and fiber microcellular structure, load different flame retardant respectively, different characteristics fire retardant combined, realize collaboration resistance
Fuel efficiency fruit.
The purpose of the present invention is achieved by following technical proposals.
Fire-retardant galapectite-montmorillonite Composite aerogel material 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, after ultrasonic disperse is uniform, vacuum is kept after vacuumizing, is then restored to normal pressure, after repeating vacuum step three times, by product
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 is at least
50h, washing are dispersed in 100 parts by weight water, obtain the dispersion liquid of step 1；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole hundred
Score (i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-
The poly dimethyl divinylsiloxanes of 5% amino list sealing end or the poly dimethyl divinyl silicon oxygen of amino bi-end-blocking
Alkane is purchased from Dow corning company.
Step 2, by after 0.08-12 parts by weight montmorillonite drying, dispersed with the montmorillonite that solvent is configured to 0.08-24wt%
Liquid, montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the dispersion liquid of step 2；
Step 3, by the dispersion liquid of 0.8-12 parts by weight step 1, the dispersion liquid of 0.7-32 parts by weight step 2,0.4-16 weight
Bis- (diphenyl phosphate) the solution mixing of bis-phenol that part mass fraction is 0.05-18wt% are measured, are scattered in decentralized medium, thereto
0.01-2 parts by weight initiator is added, after mixing evenly, warming-in-water to initiated polymerization at 70-90 DEG C, when polymerization reaction
Between after at least 37h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 10-300 DEG C of temperature and air pressure
Supercritical drying at least 1h is carried out under 1-20MPa, and fire-retardant galapectite-montmorillonite Composite aerogel material can be obtained.
In step 1,1-10 parts by weight halloysite nanotubes are added to ultrasonic disperse in the mixed solution of water and ethyl alcohol
1h, by 1-10 parts by weight of styrene sodium sulfonate, the poly- divinylsiloxanes of 0.1-1 parts by weight, 0.01-0.1 parts by weight initiator,
0.1-5 parts by weight 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 20-35min, vacuum 0.5-2h, the choosing when carrying out polymerization reaction are kept after vacuumizing
It selects and 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 will
It successively polymerize 2-8h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively.
In step 2, montmorillonite drying condition: 60-180 DEG C of temperature, time 5-20h, after the drying of 0.1-10 parts by weight
Montmorillonite be configured to the montmorillonite dispersions that mass fraction is 0.1-20wt% with solvent, by montmorillonite dispersions at 5-35 DEG C
Under 4-10h, then the ultrasonic treatment 6-15h with 50-300W power stirred with the speed mechanical of 150-400r/min.
In step 3, by the dispersion liquid of 1-10 parts by weight step 1, the dispersion liquid of 1-30 parts by weight step 2 and 0.5-15 weight
Bis- (diphenyl phosphate) the solution mixing of bis-phenol that part mass fraction is 0.05-15wt% are measured, the dispersion of 10-1000 parts by weight is scattered in
In medium, 0.01-1 parts by weight initiator is added, stirs 1h, water bath condition of the selection at 70-90 DEG C when carrying out polymerization reaction
It polymerize 12-24h in 30-50 DEG C of water bath with thermostatic control after lower prepolymerization 30-60min, then by it successively at 80 DEG C, 90 DEG C, 100
DEG C water bath with thermostatic control in polymerize 2-8h, supercritical drying time 2-4h, preferably 3h respectively.
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 galapectite-montmorillonite Composite aerogel material, true by taking out
After empty, washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed crosslinking inside halloysite nanotubes
Hexabromocyclododecane is supported in halloysite nanotubes by structure, and step 3 to be located at outside halloysite nanotubes hollow structure
It polymerize under the action of initiator between vinyl functional group in poly- divinylsiloxanes, so that halloysite nanotubes
Tridimensional network is collectively formed with poly- divinylsiloxanes, the montmorillonite being added in step 2 is successfully configured to network pore
Structure, above-mentioned tridimensional network and montmorillonite 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 galapectite-montmorillonite Composite aerogel material, while will be double
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 602.14m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, surveys through multiple groups
The average specific surface area for measuring material is 600-605m2g-1。
By N2Data in adsorption-desorption curve are substituted into correlation values, can be arranged by BJH formula and Kelvin equation
Obtain the accounting equation r in aperturek=-0.963/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.361 [- 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
12.32nm, another kind are 5.59 μm, are measured through multiple groups, and nanoscale hole is average up to 10-14nm, and micro-meter scale hole is flat
Up to 3-7 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 MMT lamella is successfully configured to network
Pore structure, aperture size is in mesoporous scale.It is overlapped to form three-dimensional netted HNTs and is uniformly dispersed in MMT three-dimensional network hole
In, realize the building of dual load system.
Detailed description of the invention
Fig. 1 is fire-retardant galapectite-montmorillonite Composite aerogel material N2Adsorption-desorption curve；
Fig. 2 is fire-retardant galapectite-montmorillonite Composite aerogel material electromicroscopic photograph.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1
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 10g sodium styrene sulfonate, 0.5g poly- divinylsiloxanes (number-average molecular weight 2700, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 2.5%), 0.6g dibenzoyl peroxide (BPO),
0.3g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 13min, is added to galapectite point
In dispersion liquid, ultrasonic disperse 20min keeps 2h 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 56min at 50 DEG C
It polymerize 15 hours in water bath with thermostatic control, it, will after it is successively then polymerize 5h 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 dispersion liquid A；11h is dried into 10g montmorillonite at 180 DEG C, then is matched with solvent
It is set to the montmorillonite dispersions that mass fraction is 20wt%；By montmorillonite dispersions with the speed mechanical of 165r/min at 30 DEG C
4h is stirred, then with the ultrasonic treatment 14h of 226W power, obtains dispersion liquid B；By 2g dispersion liquid A, 22g dispersion liquid B, 5.5g mass
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol that score is 10wt%, are scattered in 1000g decentralized medium, 0.01g peroxide are added
Change dibenzoyl (BPO), stirring 1h is placed on prepolymerization 39min under 88 DEG C of water bath condition, then in 42 DEG C of water bath with thermostatic control
It is then successively respectively placed obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, by product by middle polymerization 19h
It is placed in CO2In supercritical high-pressure extraction device, with CO2Supercritical drying is carried out at 189 DEG C of temperature and air pressure 1MPa for medium
The multiple dimensioned carrier aeroge of galapectite/montmorillonite can be obtained in 3h.
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, (number-average molecular weight 800, contents of ethylene rubs the poly- divinylsiloxanes of 0.3g
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of your percentage 3.5%), 1g dibenzoyl peroxide (BPO), 0.5g
Hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 24min, is added to galapectite dispersion liquid
In, ultrasonic disperse 35min 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 75 DEG C of water bath condition after prepolymerization 45min in 50 DEG C of perseverance
It polymerize 24 hours in tepidarium, after it is successively then polymerize 8h respectively 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 dispersion liquid A；20h is dried into 3.4g montmorillonite at 60 DEG C, then is configured with solvent
The montmorillonite dispersions for being 0.1wt% at mass fraction；By montmorillonite dispersions with the speed mechanical of 293r/min at 19 DEG C
5h is stirred, then with the ultrasonic treatment 9h of 300W power, obtains dispersion liquid B；By 1g dispersion liquid A, 12g dispersion liquid B, 8.6g mass point
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol that number is 0.65wt%, are scattered in 10g decentralized medium, 0.3g peroxidating two are added
Benzoyl (BPO), stirring 1h are placed on prepolymerization 60min under 70 DEG C of water bath condition, then gather in 30 DEG C of water bath with thermostatic control
23h is closed, it is successively respectively then placed into obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, place the product in
CO2In supercritical high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 55 DEG C of temperature and air pressure 3MPa for medium, can be obtained
To the multiple dimensioned carrier aeroge of galapectite/montmorillonite.
Embodiment 3
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 4g sodium styrene sulfonate, (number-average molecular weight 500, contents of ethylene rubs the poly- divinylsiloxanes of 0.4g
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of your percentage 5%), 0.44g dibenzoyl peroxide (BPO), 5g
Hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 34min, is added to galapectite dispersion liquid
In, ultrasonic disperse 22min 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 20 hours in water-bath, after it is successively then polymerize 6h 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 dispersion liquid A；5h is dried into 2.6g montmorillonite at 95 DEG C, then is configured to matter with solvent
Measure the montmorillonite dispersions that score is 8wt%；Montmorillonite dispersions are stirred into 8h at 25 DEG C with the speed mechanical of 400r/min,
The ultrasonic treatment 6h for using 120W power again, obtains dispersion liquid B；It is by 6g dispersion liquid A, 3g dispersion liquid B, 0.5g mass fraction
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol of 0.05wt%, are scattered in 562g decentralized medium, 0.9g diphenyl peroxide are added
Formyl (BPO), stirring 1h are placed on prepolymerization 55min under 71 DEG C of water bath condition, then polymerize in 32 DEG C of water bath with thermostatic control
It is then successively respectively placed obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control by 90h, and place the product in CO2
In supercritical high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 16 DEG C of temperature and air pressure 15MPa for medium, can be obtained
To the multiple dimensioned carrier aeroge of galapectite/montmorillonite.
Embodiment 4
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 6g sodium styrene sulfonate, 0.1g poly- divinylsiloxanes (number-average molecular weight 5000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 0.1%), 0.01g dibenzoyl peroxide
(BPO), 0.22g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 60min, is added to
In galapectite dispersion liquid, ultrasonic disperse 26min keeps 1.5h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats
Vacuum step three times after, after product is washed, be scattered in 100g water, be placed in prepolymerization 55min under 75 DEG C of water bath condition
It polymerize in 50 DEG C of water bath with thermostatic control afterwards 12 hours, then successively distinguishes it in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After polymerizeing 2h, after product is washed, it is scattered in 100g water, obtains dispersion liquid A；6h is dried into 0.1g montmorillonite at 144 DEG C,
The montmorillonite dispersions that mass fraction is 4.6wt% are configured to solvent again；By montmorillonite dispersions at 5 DEG C with 256r/min
Speed mechanical stir 10h, then with the ultrasonic treatment 15h of 260W power, obtain dispersion liquid B；5.3g dispersion liquid A, 1g are dispersed
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol that liquid B, 0.89g mass fraction is 15wt%, are scattered in 352g decentralized medium, add
Enter 0.06g dibenzoyl peroxide (BPO), stirring 1h is placed on prepolymerization 53min under 90 DEG C of water bath condition, then at 50 DEG C
Water bath with thermostatic control in polymerize 16h, be made molten after it is successively respectively then placed 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
Liquid, place the product in CO2In supercritical high-pressure extraction device, with CO2Surpassed at 300 DEG C of temperature and air pressure 20MPa for medium
The multiple dimensioned carrier aeroge of galapectite/montmorillonite can be obtained in critical dry 3h.
Embodiment 5
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 5g sodium styrene sulfonate, 0.7g poly- divinylsiloxanes (number-average molecular weight 4000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 1.5%), 0.7g azodiisobutyronitrile (ABIN),
0.1g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 29min, is added to galapectite point
In dispersion liquid, ultrasonic disperse 32min keeps 0.5h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, and repetition vacuumizes step
Suddenly three times after, after product is washed, be scattered in 100g water, be placed under 75 DEG C of water bath condition after prepolymerization 31min at 50 DEG C
Water bath with thermostatic control in polymerize 13 hours, after it is successively then polymerize 4h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control,
It after product is washed, is scattered in 100g water, obtains dispersion liquid A；18h is dried into 6.5g montmorillonite at 120 DEG C, then uses solvent
It is configured to the montmorillonite dispersions that mass fraction is 18wt%；By montmorillonite dispersions with the speed machine of 332r/min at 35 DEG C
Tool stirs 3h, then with the ultrasonic treatment 8h of 250W power, obtains dispersion liquid B；By 10g dispersion liquid A, 9g dispersion liquid B, 15g mass
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol that score is 5.2wt%, are scattered in 152g decentralized medium, it is different that 1g azo two are added
Butyronitrile (ABIN), stirring 1h are placed on prepolymerization 30min under 76 DEG C of water bath condition, then polymerize in 48 DEG C of water bath with thermostatic control
It is then successively respectively placed obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control by 15h, and place the product in CO2
In supercritical high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 225 DEG C of temperature and air pressure 4MPa for medium, can be obtained
To the multiple dimensioned carrier aeroge of galapectite/montmorillonite.
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 8g sodium styrene sulfonate, (number-average molecular weight 3000, contents of ethylene rubs the poly- divinylsiloxanes of 1g
The poly dimethyl divinylsiloxanes of the amino list sealing end of your percentage 2.5%), 0.5g azodiisobutyronitrile (ABIN),
3.5g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 10min, is added to galapectite point
In dispersion liquid, ultrasonic disperse 34min keeps 2h 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 in water bath with thermostatic control 21 hours, it, will 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
After product washing, it is scattered in 100g water, obtains dispersion liquid A；15h is dried into 3g montmorillonite at 66 DEG C, then is configured with solvent
The montmorillonite dispersions for being 0.5wt% at mass fraction；Montmorillonite dispersions are stirred at 6 DEG C with the speed mechanical of 150r/min
It mixes 9h, then with the ultrasonic treatment 12h of 50W power, obtains dispersion liquid B；By 9g dispersion liquid A, 30g dispersion liquid B, 2.6g mass fraction
For bis- (diphenyl phosphate) the solution mixing of bis-phenol of 13wt%, it is scattered in 998g decentralized medium, two isobutyl of 0.65g azo is added
Nitrile (ABIN), stirring 1h are placed on prepolymerization 44min under 85 DEG C of water bath condition, then polymerize in 35 DEG C of water bath with thermostatic control
It is then successively respectively placed obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control by 28h, and place the product in CO2
In supercritical high-pressure extraction device, with CO2Supercritical drying 3h is carried out at 10 DEG C of temperature and air pressure 10MPa for medium, can be obtained
To the multiple dimensioned carrier aeroge of galapectite/montmorillonite.
Embodiment 7
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 2000, vinyl
The poly dimethyl divinylsiloxanes of the amino list sealing end of content mole percent 3%), 0.01g azodiisobutyronitrile
(ABIN), 0.08g hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 24min, is added to
In galapectite dispersion liquid, ultrasonic disperse 28min 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 45min
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 dispersion liquid A；20h is dried into 0.08g montmorillonite at 60 DEG C,
The montmorillonite dispersions that mass fraction is 0.08wt% are configured to solvent again；By montmorillonite dispersions with 293r/ at 19 DEG C
The speed mechanical of min stirs 5h, then with the ultrasonic treatment 9h of 300W power, obtains dispersion liquid B；By 0.8g dispersion liquid A, 0.7g points
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol that dispersion liquid B, 0.4g mass fraction is 0.05wt%, are scattered in 10g decentralized medium,
It is added 0.01g azodiisobutyronitrile (ABIN), stirring 1h is placed on prepolymerization 60min under 70 DEG C of water bath condition, then 30
DEG C water bath with thermostatic control in polymerize 23h, then it is successively respectively placed in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control and is made after 2h
Solution, place the product in CO2In supercritical high-pressure extraction device, with CO2Surpassed at 10 DEG C of temperature and air pressure 1MPa for medium
The multiple dimensioned carrier aeroge of galapectite/montmorillonite can be obtained in critical dry 4h.
Embodiment 8
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 1000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of mole percent 4%), 0.3g azodiisobutyronitrile (ABIN), 8g
Hexabromocyclododecane is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 29min, is added to galapectite dispersion liquid
In, ultrasonic disperse 26min 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 80 DEG C of water bath condition after prepolymerization 31min in 60 DEG C of constant temperature
It polymerize 13 hours in water-bath, after it is successively then polymerize 4h 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 dispersion liquid A；18h is dried into 12g montmorillonite at 120 DEG C, then is configured to solvent
Mass fraction is the montmorillonite dispersions of 24wt%；Montmorillonite dispersions are stirred at 35 DEG C with the speed mechanical of 332r/min
3h, then with the ultrasonic treatment 8h of 250W power, obtain dispersion liquid B；It is by 12g dispersion liquid A, 32g dispersion liquid B, 18g mass fraction
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol of 18wt%, are scattered in 152g decentralized medium, 1.2g azodiisobutyronitrile are added
(ABIN), stirring 1h is placed on prepolymerization 30min under 76 DEG C of water bath condition, then polymerize 15h in 48 DEG C of water bath with thermostatic control,
It is successively respectively then placed into obtained solution after 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, place the product in CO2It is super to face
In boundary's high-pressure extraction device, with CO2Supercritical drying 2h is carried out at 295 DEG C of temperature and air pressure 19MPa for medium, can be obtained angstrom
The multiple dimensioned carrier aeroge of Lip river stone/montmorillonite.
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
| Embodiment | Limit oxygen index (%) | Maximum heatrelease rate (kW/m2) | Ignitor firing time (s) |
| Blank | 18 | 722 | 95 |
| Embodiment 1 | 97 | 223 | 228 |
| Embodiment 2 | 91 | 231 | 210 |
| Embodiment 3 | 83 | 218 | 231 |
| Embodiment 4 | 73 | 240 | 217 |
| Embodiment 5 | 98 | 235 | 239 |
| Embodiment 6 | 90 | 228 | 218 |
| Embodiment 7 | 92 | 232 | 221 |
| Embodiment 8 | 75 | 248 | 222 |
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-montmorillonite Composite aerogel material, it is characterised in that: galapectite-montmorillonite Composite aerogel material
Average specific surface area is 600-605m2g-1, nanoscale and micron are existed simultaneously in galapectite-montmorillonite Composite aerogel material
Pore dimension, nanoscale hole average out to 10-14nm, carries out as steps described below by 3-7 μm of average out to of micro-meter scale hole:
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,
After ultrasonic disperse is uniform, vacuum is kept after vacuumizing, 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 percent
(i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-5%'s
The poly dimethyl divinylsiloxanes of amino list sealing end or the poly dimethyl divinylsiloxanes of amino bi-end-blocking；
Step 2, by after 0.08-12 parts by weight montmorillonite drying, the montmorillonite dispersions of 0.08-24wt% are configured to solvent,
Montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the dispersion liquid of step 2；
Step 3, by the dispersion liquid of 0.8-12 parts by weight step 1, the dispersion liquid of 0.7-32 parts by weight step 2,0.4-16 parts by weight
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol that mass fraction is 0.05-18wt%, are scattered in decentralized medium, are added thereto
0.01-2 parts by weight initiator, after mixing evenly, warming-in-water to initiated polymerization at 70-90 DEG C, polymerization reaction time is extremely
After few 37h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 10-300 DEG C of temperature and air pressure 1-
Supercritical drying at least 1h is carried out under 20MPa, and fire-retardant galapectite-montmorillonite Composite aerogel material can be obtained；
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-montmorillonite Composite aerogel material, by vacuumizing, washing
After washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed cross-linked structure inside halloysite nanotubes,
Hexabromocyclododecane is supported in halloysite nanotubes, step 3 makes be located at outside halloysite nanotubes hollow structure poly- two
It polymerize under the action of initiator between vinyl functional group on vinylsiloxane, so that halloysite nanotubes and poly-
Tridimensional network is collectively formed in divinylsiloxanes, and the montmorillonite being added in step 2 is successfully configured to network pore structure,
Above-mentioned tridimensional network and montmorillonite are successfully configured to network pore structure and together form three-dimensional network pore structure, above-mentioned
Three-dimensional network pore structure provides meso-hole structure for fire-retardant galapectite-montmorillonite Composite aerogel material, while by the bis- (phosphorus of bis-phenol
Diphenyl phthalate) it is supported in meso-hole structure.
2. fire-retardant galapectite-montmorillonite Composite aerogel material 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 20-35min keeps vacuum 0.5-2h, water of the selection at 70-80 DEG C when carrying out polymerization reaction after vacuumizing
It polymerize 12-24h under the conditions of bath 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 galapectite-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step 2
In, montmorillonite drying condition: 60-180 DEG C of temperature, time 5-20h, montmorillonite solvent of the 0.1-10 parts by weight after dry is matched
The montmorillonite dispersions that mass fraction is 0.1-20wt% are set to, by montmorillonite dispersions with 150-400r/min at 5-35 DEG C
Speed mechanical stir 4-10h, then the ultrasonic treatment 6-15h with 50-300W power.
4. fire-retardant galapectite-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: in step 3
In, it is by the dispersion liquid of 1-10 parts by weight step 1, the dispersion liquid of 1-30 parts by weight step 2 and 0.5-15 parts by weight mass fraction
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol of 0.05-15wt%, are scattered in 10-1000 parts by weight decentralized medium, are added
0.01-1 parts by weight initiator stirs 1h, selection prepolymerization 30- under 70-90 DEG C of water bath condition when carrying out polymerization reaction
It polymerize 12-24h after 60min in 30-50 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C of thermostatted water
It polymerize 2-8h, supercritical drying time 2-4h, preferably 3h in bath respectively.
5. fire-retardant galapectite-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: initiator choosing
Select dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
6. fire-retardant galapectite-montmorillonite Composite aerogel material preparation method, it is characterised in that: carry out as steps described below:
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,
After ultrasonic disperse is uniform, vacuum is kept after vacuumizing, 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 percent
(i.e. the ratio of the poly dimethyl divinylsiloxanes molal quantity of vinyl molal quantity and entire amino list sealing end) 0.1-5%'s
The poly dimethyl divinylsiloxanes of amino list sealing end or the poly dimethyl divinylsiloxanes of amino bi-end-blocking；
Step 2, by after 0.08-12 parts by weight montmorillonite drying, the montmorillonite dispersions of 0.08-24wt% are configured to solvent,
Montmorillonite dispersions mechanical stirring is uniform, after being then sonicated, obtain the dispersion liquid of step 2；
Step 3, by the dispersion liquid of 0.8-12 parts by weight step 1, the dispersion liquid of 0.7-32 parts by weight step 2,0.4-16 parts by weight
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol that mass fraction is 0.05-18wt%, are scattered in decentralized medium, are added thereto
0.01-2 parts by weight initiator, after mixing evenly, warming-in-water to initiated polymerization at 70-90 DEG C, polymerization reaction time is extremely
After few 37h, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium in 10-300 DEG C of temperature and air pressure 1-
Supercritical drying at least 1h is carried out under 20MPa, and fire-retardant galapectite-montmorillonite Composite aerogel material can be obtained；
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-montmorillonite Composite aerogel material, by vacuumizing, washing
After washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed cross-linked structure inside halloysite nanotubes,
Hexabromocyclododecane is supported in halloysite nanotubes, step 3 makes be located at outside halloysite nanotubes hollow structure poly- two
It polymerize under the action of initiator between vinyl functional group on vinylsiloxane, so that halloysite nanotubes and poly-
Tridimensional network is collectively formed in divinylsiloxanes, and the montmorillonite being added in step 2 is successfully configured to network pore structure,
Above-mentioned tridimensional network and montmorillonite are successfully configured to network pore structure and together form three-dimensional network pore structure, above-mentioned
Three-dimensional network pore structure provides meso-hole structure for fire-retardant galapectite-montmorillonite Composite aerogel material, while by the bis- (phosphorus of bis-phenol
Diphenyl phthalate) it is supported in meso-hole structure.
7. the preparation method of fire-retardant galapectite-montmorillonite Composite aerogel material 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 20-35min keeps vacuum 0.5-2h 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 galapectite-montmorillonite Composite aerogel material according to claim 6, feature exist
In: in step 2, montmorillonite drying condition: 60-180 DEG C of temperature, time 5-20h, illiteracy of the 0.1-10 parts by weight after dry is taken off
Soil is configured to the montmorillonite dispersions that mass fraction is 0.1-20wt% with solvent, by montmorillonite dispersions at 5-35 DEG C with
The speed mechanical of 150-400r/min stirs 4-10h, then the ultrasonic treatment 6-15h with 50-300W power.
9. the preparation method of fire-retardant galapectite-montmorillonite Composite aerogel material according to claim 6, feature exist
In: in step 3, by the dispersion liquid of 1-10 parts by weight step 1, the dispersion liquid of 1-30 parts by weight step 2 and 0.5-15 parts by weight
Bis- (diphenyl phosphate) the solution mixing of the bis-phenol that mass fraction is 0.05-15wt%, are scattered in 10-1000 parts by weight decentralized medium
In, 0.01-1 parts by weight initiator is added, stirs 1h, selection is pre- under 70-90 DEG C of water bath condition when carrying out polymerization reaction
It polymerize 12-24h after polyase 13 0-60min in 30-50 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C, 100 DEG C
It polymerize 2-8h, supercritical drying time 2-4h, preferably 3h in water bath with thermostatic control respectively.
10. the preparation method of fire-retardant galapectite-montmorillonite Composite aerogel material according to claim 6, feature exist
In: initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710986549.6A CN109694539A (en) | 2017-10-20 | 2017-10-20 | Fire-retardant galapectite-montmorillonite Composite aerogel material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710986549.6A CN109694539A (en) | 2017-10-20 | 2017-10-20 | Fire-retardant galapectite-montmorillonite Composite aerogel material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109694539A true CN109694539A (en) | 2019-04-30 |
Family
ID=66225409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710986549.6A Pending CN109694539A (en) | 2017-10-20 | 2017-10-20 | Fire-retardant galapectite-montmorillonite Composite aerogel material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109694539A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113528156A (en) * | 2021-07-13 | 2021-10-22 | 浙江理工大学 | Preparation method of halloysite-hydroxyapatite-nanocellulose fiber composite flame-retardant material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241889A (en) * | 2010-09-20 | 2011-11-16 | 深圳市科聚新材料有限公司 | Halloysite composite flame retardant masterbatch |
| CN102532597A (en) * | 2010-12-24 | 2012-07-04 | 中国石油化工股份有限公司 | Halloysite/montmorillonoid composite powder and preparation method and application thereof |
| CN103232851A (en) * | 2013-04-15 | 2013-08-07 | 西北师范大学 | Montmorillonite composite fire retardant |
| CN103599734A (en) * | 2013-11-22 | 2014-02-26 | 中国工程物理研究院核物理与化学研究所 | Aerogel material and preparation method thereof |
| WO2015149975A1 (en) * | 2014-04-02 | 2015-10-08 | L'oreal | Depilatory compositions |
| CN105565774A (en) * | 2015-05-11 | 2016-05-11 | 天津城建大学 | High-strength high-thermal-insulation silica aerogel and preparation method thereof |
-
2017
- 2017-10-20 CN CN201710986549.6A patent/CN109694539A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241889A (en) * | 2010-09-20 | 2011-11-16 | 深圳市科聚新材料有限公司 | Halloysite composite flame retardant masterbatch |
| CN102532597A (en) * | 2010-12-24 | 2012-07-04 | 中国石油化工股份有限公司 | Halloysite/montmorillonoid composite powder and preparation method and application thereof |
| CN103232851A (en) * | 2013-04-15 | 2013-08-07 | 西北师范大学 | Montmorillonite composite fire retardant |
| CN103599734A (en) * | 2013-11-22 | 2014-02-26 | 中国工程物理研究院核物理与化学研究所 | Aerogel material and preparation method thereof |
| WO2015149975A1 (en) * | 2014-04-02 | 2015-10-08 | L'oreal | Depilatory compositions |
| CN105565774A (en) * | 2015-05-11 | 2016-05-11 | 天津城建大学 | High-strength high-thermal-insulation silica aerogel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 尹洪峰等: "《功能复合材料》", 31 August 2013, 冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113528156A (en) * | 2021-07-13 | 2021-10-22 | 浙江理工大学 | Preparation method of halloysite-hydroxyapatite-nanocellulose fiber composite flame-retardant material |
| CN113528156B (en) * | 2021-07-13 | 2022-09-30 | 浙江理工大学 | Preparation method of halloysite-hydroxyapatite-nanocellulose fiber composite flame-retardant material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101671149B (en) | Paraffin microencapsulated phase-change thermal-storage mortar and preparation method thereof | |
| CN101348626B (en) | Temperature adjustment coating and preparation thereof | |
| CN105418820B (en) | Cinepazid polymer/SiO of hydroxyl2Hybridisation emulsion and the preparation method and application thereof | |
| CN102618016B (en) | Light-transparent heat insulating film, its preparation method and application | |
| CN111303355A (en) | Silica Janus colloidal particles and preparation method and application thereof | |
| CN107353764B (en) | A kind of energy storage multifunctional coating and preparation method thereof | |
| CN109694539A (en) | Fire-retardant galapectite-montmorillonite Composite aerogel material and preparation method thereof | |
| CN109694447A (en) | Multiple dimensioned galapectite-montmorillonite Composite aerogel material and preparation method thereof | |
| CN109081354A (en) | Fire-retardant galapectite-silicon dioxide composite aerogel material and preparation method thereof | |
| CN108997538A (en) | Fire-retardant galapectite aerogel material and preparation method thereof | |
| CN106565198A (en) | A method of preparing flexible aerosil through atmospheric-pressure drying | |
| CN109694449A (en) | With mesoporous and micropore netted galapectite-montmorillonite Composite aerogel material and preparation method thereof | |
| CN109692631A (en) | Three-dimensional netted galapectite-montmorillonite Composite aerogel material and preparation method thereof | |
| CN109692632A (en) | Fire-retardant graphene-galapectite aerogel composite and preparation method thereof | |
| CN109988274A (en) | With mesoporous and micropore mesh carbon nanotube-galapectite aerogel composite and preparation method thereof | |
| CN109694448A (en) | With mesoporous and micropore graphene net-galapectite aerogel composite and preparation method thereof | |
| CN109692149A (en) | Galapectite-montmorillonite Composite aerogel material and preparation method thereof | |
| CN108969467A (en) | Galapectite aerogel material and preparation method thereof | |
| CN109692148A (en) | Three-dimensional netted graphene-galapectite aerogel composite and preparation method thereof | |
| CN108976360A (en) | Three-dimensional netted galapectite aerogel material and preparation method thereof | |
| CN112574568A (en) | Phase-change temperature-control silicone rubber composition and preparation method thereof | |
| CN109692152A (en) | Graphene-galapectite aerogel composite and preparation method thereof | |
| CN109692633A (en) | Fire-retardant carbon nanotube-galapectite aerogel composite and preparation method thereof | |
| CN109010250A (en) | Galapectite-silicon dioxide composite aerogel material and preparation method thereof | |
| CN108997539A (en) | Multiple dimensioned galapectite aerogel material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190430 |