CN108997538A - Fire-retardant galapectite aerogel material and preparation method thereof - Google Patents
Fire-retardant galapectite aerogel material and preparation method thereof Download PDFInfo
- Publication number
- CN108997538A CN108997538A CN201710418641.2A CN201710418641A CN108997538A CN 108997538 A CN108997538 A CN 108997538A CN 201710418641 A CN201710418641 A CN 201710418641A CN 108997538 A CN108997538 A CN 108997538A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- galapectite
- retardant
- fire
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08K5/02—Halogenated hydrocarbons
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Colloid Chemistry (AREA)
Abstract
The present invention provides fire-retardant galapectite aerogel material and preparation method thereof, after galapectite dispersion liquid is polymerize with the mixed solution of hexabromocyclododecane, after bis-phenol bis- (diphenyl phosphates) and initiator are added into polymerizate again, polymerization reaction is carried out again, obtains fire-retardant galapectite aerogel material.The beneficial effects of the invention are as follows use the doughnut with microcellular structure for raw material, build three-dimensional aeroge network, utilize the meso-hole structure of aeroge and the microcellular structure of fiber, load hexabromocyclododecane and bis-phenol are bis- (diphenyl phosphate) respectively, different characteristics fire retardant is combined, realizes cooperative flame retardant effect.
Description
Technical field
The invention belongs to technical field of nano material, more particularly, are related to a kind of fire-retardant galapectite aerogel material
And preparation method thereof.
Background technique
Galapectite is natural one of clay mineral, belongs to kaolinic mutation, therefore also referred to as metakaolin.It is
It is crimped under field conditions (factors) by kaolinic lamella, main existence form is nanotube-shaped (Ma Zhi, king in nature
Gold leaf, Gao Xiang, Ding Tong, application study status [J] chemical progress of Qin Yongning halloysite nanotubes, 2012, (Z1): 275-
283.).Galapectite mine is distributed in each continent in the whole world, the countries such as China, France, Belgium, New Zealand, the U.S., Turkey
There are reserves abundant.Galapectite mine is mainly distributed on Guangdong, Hubei, Hunan, Sichuan, Guizhou, Yunnan, Shanxi etc. in China and saves
Part.
Galapectite is the double-deck 1:1 type aluminosilicate material, has typical crystalline texture.Galapectite is different from kaolinic
Substantive characteristics is that galapectite interlayer exists or once there is the crystallization water, and the lamella of galapectite is the oxygen-octahedron by outer layer
It is formed with the alumina octahedral regular array of internal layer, is free hydrone among lamella.These hydrones are easy to slough, this
Dehydration is irreversible.The outer surface of galapectite is mainly Si-O-Si key composition, and inner wall is then mainly aluminium hydroxyl (Niu Ji
South, Qiang Yinghuai, Wang Chunyang, Li Xiang, Monday is great, Shang Xiangyu, 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 deficiency in the prior art, a kind of fire-retardant galapectite aerogel material and its preparation side are provided
Method uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, using aeroge meso-hole structure and
The microcellular structure of fiber, loads different flame retardant respectively, and different characteristics fire retardant is combined, and realizes cooperative flame retardant effect.
The purpose of the present invention is achieved by following technical proposals.
Fire-retardant galapectite aerogel material and preparation method thereof carries out as steps described below:
Step 1,0.8-18 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 0.8-18 parts by weight of styrene sodium sulfonate, 0.07-1.8
The poly- divinylsiloxanes of parts by weight, 0.01-0.45 parts by weight initiator, 0.05-9 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 in galapectite dispersion liquid after stirring,
Ultrasonic disperse is uniform, and vacuum is kept after vacuumizing, and is then restored to normal pressure, and after repetition vacuumizes three times, washing obtains step 1
Product；
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, it disperses step 1 product in 100 parts by weight water, warming-in-water to 52-78 DEG C of initiated polymerization, gathers
The conjunction reaction time is at least 48h, obtains step 2 product；
Step 3, it will be scattered in 100 parts by weight water after the washing of step 2 product, the bis-phenol that 0.07-18 parts by weight are added is double
(diphenyl phosphate) and 0.01-1.6 parts by weight initiator, after mixing evenly, warming-in-water to 64-98 DEG C of initiated polymerization,
Polymerization reaction time is at least 36h, and fire-retardant galapectite hydrogel is made；
Initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN)；
Step 4, fire-retardant galapectite hydrogel is placed in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature
Supercritical drying at least 1h is carried out under 5-350 DEG C and air pressure 0.5-30MPa, and fire-retardant galapectite aerogel material can be obtained.
In step 1, halloysite nanotubes are 1.5-9 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol and surpass
Sound disperses 1h, and sodium styrene sulfonate is 1.5-9 parts by weight, and poly- divinylsiloxanes are 0.15-0.9 parts by weight, and initiator is
0.01-0.1 parts by weight, hexabromocyclododecane are 0.2-4.6 parts by weight, are added in the mixed liquor of deionized water and ethyl alcohol and stir
It after 12-56min, is added in galapectite dispersion liquid, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor.
In step 2, selection polyase 13 0-60min at 52-78 DEG C when carrying out polymerization reaction, is then cooled to 12-56
It polymerize 12-24h at DEG C, then successively polymerize 2.5-7.5h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
In step 3,0.15-14 parts by weight of bisphenol bis- (diphenyl phosphates) and 0.01-1 weight are added into above-mentioned dispersion liquid
It measures part initiator and stirs 1h, selection polymerize 20-50min at 64-98 DEG C when carrying out polymerization reaction, is then cooled to 32-68
It polymerize 20-30h at DEG C, then successively polymerize 1-3h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
In step 4, the time for carrying out supercritical drying is 2-4h, preferably 3h.
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 aerogel material, by vacuumizing, washing, in step
Poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate in rapid 2, 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 above-mentioned tridimensional network provides for fire-retardant galapectite aerogel material
Meso-hole structure, while bis-phenol bis- (diphenyl phosphates) being 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 N2 adsorption-desorption curve of the tester analysis composite material that according to the present invention prepared by the method, 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
Group measurement average specific surface area is up to 601-606m2g-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=-0.961/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.362 [- 5/
ln(p/p0)] ^ (1/3), can obtain effective aperture is r=rk+ t, therefore aperture is the function influenced by relative pressure, so may be used
In the hope of the aperture under different relative pressures, it can calculate and acquire in material that there are two aperture points to be distributed, Yi Zhongwei
10.29nm, another kind are 20.39 μm, and average up to 10-11nm through multiple groups measurement nanoscale hole, micro-meter scale hole is flat
Up to 20-21 μm.It can be seen that material exists simultaneously nanoscale and micro-meter scale hole.
Using the Nanosem430 field emission scanning electron microscope of Dutch Philips to the method for the invention system of utilization
The microscopic appearance of standby composite material is observed, as shown in Figure 2.It can be seen from the figure that the success of halloysite nanotubes fiber
It is configured to network pore structure, aperture size is in mesoporous scale.In conjunction with halloysite nanotubes inner wall microcellular structure, realize double
The building of heavy duty system.
Detailed description of the invention
Fig. 1 is the N of fire-retardant galapectite aerogel material2Adsorption-desorption curve；
Fig. 2 is the electromicroscopic photograph of fire-retardant galapectite aerogel material.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1.
5 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 10 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.3 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%),
0.07 parts by weight dibenzoyl peroxide (BPO), 3 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, 50min 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 70 DEG C of water bath condition after prepolymerization 24min and polymerize 19 hours in 20 DEG C of water bath with thermostatic control, then will
It successively distinguishes polyase 13 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, and 100 parts by weight water are scattered in after product is washed
In, the bis-phenol bis- (diphenyl phosphates) and 0.3 parts by weight dibenzoyl peroxide (BPO) of 9 parts by weight is added, stirring 1h is placed on
Then prepolymerization 40min under 97 DEG C of water bath condition polymerize 24 hours, then by it successively 80 in 56 DEG C of water bath with thermostatic control
DEG C, 90 DEG C, fire-retardant galapectite hydrogel is made after polymerizeing 1.5h respectively in 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 3h is carried out at 20 DEG C of temperature and air pressure 12MPa for medium, can be hindered
Fire galapectite aerogel material.
Embodiment 2.
7 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 0.5 parts by weight
(number-average molecular weight 3000, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 1%),
0.01 parts by weight dibenzoyl peroxide (BPO), 5 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, 11min 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 75 DEG C of water bath condition after prepolymerization 35min and polymerize 12 hours in 54 DEG C of water bath with thermostatic control, then will
It successively polymerize 5h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively, and 100 parts by weight water are scattered in after product is washed
In, the bis-phenol bis- (diphenyl phosphates) and 0.5 parts by weight dibenzoyl peroxide (BPO) of 5 parts by weight is added, stirring 1h is placed on
Then prepolymerization 48min under 85 DEG C of water bath condition polymerize 28 hours, then by it successively 80 in 40 DEG C of water bath with thermostatic control
DEG C, 90 DEG C, fire-retardant galapectite hydrogel is made after polymerizeing 2.5h respectively in 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 3h is carried out at 10 DEG C of temperature and air pressure 14MPa for medium, can be hindered
Fire galapectite aerogel material.
Embodiment 3.
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 4 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.8 parts by weight
(number-average molecular weight 2000, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 2%),
0.1 parts by weight azodiisobutyronitrile (ABIN), 0.7 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, 13min 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 52 DEG C of water bath condition after prepolymerization 30min and polymerize 18 hours in 15 DEG C of water bath with thermostatic control, then will
It successively distinguishes polymerase 17 .5h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, and 100 parts by weight water are scattered in after product is washed
In, the bis-phenol bis- (diphenyl phosphates) and 0.7 parts by weight azodiisobutyronitrile (ABIN) of 0.1 parts by weight is added, stirs 1h postposition
The prepolymerization 35min under 90 DEG C of water bath condition, then polyase 13 0 hour in 36 DEG C of water bath with thermostatic control, then successively exists it
80 DEG C, 90 DEG C, fire-retardant galapectite hydrogel is made after polyase 13 h respectively in 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 3h is carried out at 100 DEG C of temperature and air pressure 3MPa for medium, can be hindered
Fire galapectite aerogel material.
Embodiment 4.
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 0.7 parts by weight
(number-average molecular weight 4000, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 2%),
0.03 parts by weight azodiisobutyronitrile (ABIN), 0.1 parts by weight hexabromocyclododecane are added to 50 parts by weight of deionized water and 50
In the mixed liquor of parts by weight of ethanol, 20min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, by above-mentioned mixing
Liquid keeps 1h after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, product is washed, is then dispersed in 100
In parts by weight water, it is placed under 55 DEG C of water bath condition after prepolymerization 60min in 55 DEG C of water bath with thermostatic control and polymerize 24 hours, then
It is successively polymerize 2.5h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively, 100 parts by weight are scattered in after product is washed
In water, the bis-phenol bis- (diphenyl phosphates) and 0.8 parts by weight azodiisobutyronitrile (ABIN) of 4 parts by weight is added, stirs 1h postposition
Then the prepolymerization 39min under 80 DEG C of water bath condition polymerize 20 hours in 37 DEG C of water bath with thermostatic control, then it successively exists
80 DEG C, 90 DEG C, fire-retardant galapectite hydrogel is made after polyase 13 h respectively in 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 2.5h is carried out at 300 DEG C of temperature and air pressure 5MPa for medium, can be obtained
Fire-retardant galapectite aerogel material.
Embodiment 5.
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 2 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 1 parts by weight (number
Average molecular weight 5000, the poly dimethyl divinylsiloxanes of the amino bi-end-blocking of contents of ethylene mole percent 0.1%),
0.02 parts by weight azodiisobutyronitrile (ABIN), 0.8 parts by weight hexabromocyclododecane are added to 50 parts by weight of deionized water and 50
In the mixed liquor of parts by weight of ethanol, 60min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, by above-mentioned mixing
Liquid keeps 1h after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, product is washed, is then dispersed in 100
In parts by weight water, it is placed under 60 DEG C of water bath condition after prepolymerization 20min in 19 DEG C of water bath with thermostatic control and polymerize 15 hours, then
It is successively polymerize 6h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively, 100 parts by weight water are scattered in after product is washed
In, the bis-phenol bis- (diphenyl phosphates) and 0.01 parts by weight azodiisobutyronitrile (ABIN) of 15 parts by weight is added, stirs 1h postposition
Then the prepolymerization 20min under 60 DEG C of water bath condition polymerize 27 hours in 70 DEG C of water bath with thermostatic control, then it successively exists
80 DEG C, 90 DEG C, fire-retardant galapectite hydrogel is made after polymerizeing 2h respectively in 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 3h is carried out at 150 DEG C of temperature and air pressure 20MPa for medium, can be hindered
Fire galapectite aerogel material.
Embodiment 6.
10 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 8 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 0.1 parts by weight
(number-average molecular weight 500, the poly dimethyl divinylsiloxanes of the amino list sealing end of contents of ethylene mole percent 5%),
0.05 parts by weight azodiisobutyronitrile (ABIN), 0.3 parts by weight hexabromocyclododecane are added to 50 parts by weight of deionized water and 50
In the mixed liquor of parts by weight of ethanol, 10min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, by above-mentioned mixing
Liquid keeps 1h after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, product is washed, is then dispersed in 100
In parts by weight water, it is placed under 80 DEG C of water bath condition after prepolymerization 37min in 58 DEG C of water bath with thermostatic control and polymerize 20 hours, then
It is successively polymerize 4h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively, 100 parts by weight water are scattered in after product is washed
In, the bis-phenol bis- (diphenyl phosphates) and 1 parts by weight azodiisobutyronitrile (ABIN) of 6 parts by weight is added, stirring 1h is placed on 75
DEG C water bath condition under prepolymerization 50min, then polymerize 25 hours in 45 DEG C of water bath with thermostatic control, then by it successively 80
DEG C, 90 DEG C, fire-retardant galapectite hydrogel is made after polymerizeing 1.5h respectively in 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 4h is carried out at 55 DEG C of temperature and air pressure 1MPa for medium, can be obtained fire-retardant
Galapectite aerogel material.
Embodiment 7
0.8 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 0.8 parts by weight of styrene sodium sulfonate, the poly- divinyl silicon of 0.07 parts by weight
Oxygen alkane (number-average molecular weight 2500, the poly dimethyl divinyl silicon of the amino list sealing end of contents of ethylene mole percent 2.5%
Oxygen alkane), 0.01 parts by weight dibenzoyl peroxide (BPO), 0.05 parts by weight hexabromocyclododecane be added to 50 parts by weight go from
In sub- water and the mixed liquor of 50 parts by weight of ethanol, 13min is stirred, is added in galapectite dispersion liquid, ultrasonic disperse 30min, it will
Above-mentioned mixed liquor keeps 1h after vacuumizing, be then restored to normal pressure, after repeating vacuum step three times, product is washed, then
It is scattered in 100 parts by weight water, is placed under 52 DEG C of water bath condition and polymerize 18 in 12 DEG C of water bath with thermostatic control after prepolymerization 30min
Hour, it is then successively distinguished in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control to polymerase 17 .5h, is scattered in after product is washed
In 100 parts by weight water, the bis-phenol bis- (diphenyl phosphates) and 0.01 parts by weight dibenzoyl peroxide of 0.07 parts by weight is added
(BPO), stirring 1h is placed on prepolymerization 35min under 90 DEG C of water bath condition, and then polyase 13 0 is small in 34 DEG C of water bath with thermostatic control
When, then it is successively polymerize after 2.5h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control and fire-retardant galapectite water-setting is made
Glue, place the product in CO2In supercritical high-pressure extraction device, with CO2Surpassed at 350 DEG C of temperature and air pressure 30MPa for medium
Fire-retardant galapectite aerogel material can be obtained in critical dry 2.5h.
Embodiment 8
18 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 18 parts by weight of styrene sodium sulfonates, the poly- divinylsiloxanes of 1.8 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%),
0.45 parts by weight dibenzoyl peroxide (BPO), 9 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, 60min 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 60 DEG C of water bath condition after prepolymerization 20min and polymerize 15 hours in 19 DEG C of water bath with thermostatic control, then will
It successively polymerize 6h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively, and 100 parts by weight water are scattered in after product is washed
In, the bis-phenol bis- (diphenyl phosphates) and 1.6 parts by weight dibenzoyl peroxides (BPO) of 18 parts by weight is added, stirs 1h postposition
Then the prepolymerization 20min under 60 DEG C of water bath condition polymerize 27 hours in 70 DEG C of water bath with thermostatic control, then it successively exists
80 DEG C, 90 DEG C, fire-retardant galapectite hydrogel is made after polyase 13 h respectively in 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 4h is carried out at 5 DEG C of temperature and air pressure 0.5MPa for medium, can be hindered
Fire galapectite aerogel material.
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 aerogel material, it is characterised in that: galapectite aerogel material average specific surface area is 601-
606m2g-1, nanoscale and micro-meter scale hole, nanoscale hole average out to are existed simultaneously in galapectite aerogel material
10-11nm, is carried out as steps described below by 20-21 μm of average out to of micro-meter scale hole:
Step 1,0.8-18 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 0.8-18 parts by weight of styrene sodium sulfonate, 0.07-1.8 weight
The poly- divinylsiloxanes of part, 0.01-0.45 parts by weight initiator, 0.05-9 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 stirring, ultrasound
It is uniformly dispersed, vacuum is kept after vacuumizing, be then restored to normal pressure, after repetition vacuumizes three times, washing obtains step 1 product；
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) 0.2-4.6%
Amino list sealing end poly dimethyl divinylsiloxanes or amino bi-end-blocking poly dimethyl divinylsiloxanes；
Step 2, it disperses step 1 product in 100 parts by weight water, warming-in-water to 52-78 DEG C of initiated polymerization, polymerization is anti-
It is at least 48h between seasonable, obtains step 2 product；
Step 3, it will be scattered in 100 parts by weight water after the washing of step 2 product, the bis- (phosphoric acid of bis-phenol of 0.07-18 parts by weight be added
Diphenyl ester) and 0.01-1.6 parts by weight initiator, after mixing evenly, warming-in-water to 64-98 DEG C of initiated polymerization, polymerization is instead
It is at least 36h between seasonable, fire-retardant galapectite hydrogel is made；
Step 4, fire-retardant galapectite hydrogel is placed in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature 5-350
DEG C and air pressure 0.5-30MPa under carry out supercritical drying at least 1h, fire-retardant galapectite 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 aerogel material, by vacuumizing, washing, in step 2
In poly- divinylsiloxanes be copolymerized with sodium styrene sulfonate, formed halloysite nanotubes inside formed cross-linked structure, will
Hexabromocyclododecane is supported in halloysite nanotubes, and step 3 makes the poly- diethyl being located at outside halloysite nanotubes hollow structure
It polymerize under the action of initiator between vinyl functional group in alkenyl siloxane, so that halloysite nanotubes and poly- two
Tridimensional network is collectively formed in vinylsiloxane, and above-mentioned tridimensional network provides Jie for fire-retardant galapectite aerogel material
Pore structure, while bis-phenol bis- (diphenyl phosphates) being supported in meso-hole structure.
2. fire-retardant galapectite aerogel material according to claim 1, it is characterised in that: in step 1, galapectite nanometer
Pipe is 1.5-9 parts by weight, is added to ultrasonic disperse 1h in the mixed liquor of deionized water and ethyl alcohol, sodium styrene sulfonate 1.5-9
Parts by weight, poly- divinylsiloxanes are 0.15-14 parts by weight, and initiator is 0.01-0.1 parts by weight, and hexabromocyclododecane is
0.2-4.6 parts by weight are added to after stirring 12-56min in the mixed liquor of deionized water and ethyl alcohol, are added to galapectite dispersion liquid
In, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor；Initiator select dibenzoyl peroxide (BPO) or
Azodiisobutyronitrile (ABIN).
3. fire-retardant galapectite aerogel material according to claim 1, it is characterised in that: in step 2, polymerize
Selection polyase 13 0-60min at 52-78 DEG C, is then cooled at 12-56 DEG C and polymerize 12-24h, then successively at 80 DEG C when reaction,
It polymerize 2.5-7.5h respectively at 90 DEG C and 100 DEG C.
4. fire-retardant galapectite aerogel material according to claim 1, it is characterised in that: in step 3, to above-mentioned dispersion
0.15-18 parts by weight of bisphenol bis- (diphenyl phosphates) is added in liquid and 0.01-1 parts by weight initiator stirs 1h, is being polymerize
Selection polymerize 20-50min at 64-98 DEG C when reaction, is then cooled at 32-68 DEG C and polymerize 20-30h, then successively at 80 DEG C,
It polymerize 1-3h respectively at 90 DEG C and 100 DEG C.
5. fire-retardant galapectite aerogel material according to claim 1, it is characterised in that: in step 4, carry out overcritical
The dry time is 2-4h, preferably 3h.
6. the method for preparing fire-retardant galapectite aerogel material as claimed in claim 1 to 5, it is characterised in that: according to
Following step carries out:
Step 1,0.8-18 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 0.8-18 parts by weight of styrene sodium sulfonate, 0.07-1.8 weight
The poly- divinylsiloxanes of part, 0.01-0.45 parts by weight initiator, 0.05-9 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 stirring, ultrasound
It is uniformly dispersed, vacuum is kept after vacuumizing, be then restored to normal pressure, after repetition vacuumizes three times, washing obtains step 1 product；
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) 0.2-4.6%
Amino list sealing end poly dimethyl divinylsiloxanes or amino bi-end-blocking poly dimethyl divinylsiloxanes；
Step 2, it disperses step 1 product in 100 parts by weight water, warming-in-water to 52-78 DEG C of initiated polymerization, polymerization is anti-
It is at least 48h between seasonable, obtains step 2 product；
Step 3, it will be scattered in 100 parts by weight water after the washing of step 2 product, the bis- (phosphoric acid of bis-phenol of 0.07-18 parts by weight be added
Diphenyl ester) and 0.01-1.6 parts by weight initiator, after mixing evenly, warming-in-water to 64-98 DEG C of initiated polymerization, polymerization is instead
It is at least 36h between seasonable, fire-retardant galapectite hydrogel is made；
Step 4, fire-retardant galapectite hydrogel is placed in CO2In supercritical high-pressure extraction device, with CO2It is medium in temperature 5-350
DEG C and air pressure 0.5-30MPa under carry out supercritical drying at least 1h, fire-retardant galapectite 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 aerogel material, by vacuumizing, washing, in step 2
In poly- divinylsiloxanes be copolymerized with sodium styrene sulfonate, formed halloysite nanotubes inside formed cross-linked structure, will
Hexabromocyclododecane is supported in halloysite nanotubes, and step 3 makes the poly- diethyl being located at outside halloysite nanotubes hollow structure
It polymerize under the action of initiator between vinyl functional group in alkenyl siloxane, so that halloysite nanotubes and poly- two
Tridimensional network is collectively formed in vinylsiloxane, and above-mentioned tridimensional network provides Jie for fire-retardant galapectite aerogel material
Pore structure, while bis-phenol bis- (diphenyl phosphates) being supported in meso-hole structure.
7. the preparation method of fire-retardant galapectite aerogel material according to claim 6, it is characterised in that: in step 1,
Halloysite nanotubes are 1.5-9 parts by weight, are added to ultrasonic disperse 1h, styrene sulfonic acid in the mixed liquor of deionized water and ethyl alcohol
Sodium is 1.5-9 parts by weight, and poly- divinylsiloxanes are 0.15-0.9 parts by weight, and initiator is 0.01-0.1 parts by weight, hexabromo
Cyclododecane is 0.2-4.6 parts by weight, is added to after stirring 12-56min in the mixed liquor of deionized water and ethyl alcohol, is added to angstrom
In the stone dispersion liquid of Lip river, ultrasonic disperse 30min keeps 1h after vacuumizing above-mentioned mixed liquor；Initiator selects diphenyl peroxide first
Acyl (BPO) or azodiisobutyronitrile (ABIN).
8. the preparation method of fire-retardant galapectite aerogel material according to claim 6, it is characterised in that: in step 2,
Selection polyase 13 0-60min at 52-78 DEG C when carrying out polymerization reaction, is then cooled at 12-56 DEG C and polymerize 12-24h, then
Successively it polymerize 2.5-7.5h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
9. the preparation method of fire-retardant galapectite aerogel material according to claim 6, it is characterised in that: in step 3,
0.15-14 parts by weight of bisphenol bis- (diphenyl phosphates) is added into above-mentioned dispersion liquid and 0.01-1 parts by weight initiator stirs 1h,
When carrying out polymerization reaction, selection polymerize 20-50min at 64-98 DEG C, is then cooled at 32-68 DEG C and polymerize 20-30h, then
Successively it polymerize 1-3h respectively at 80 DEG C, 90 DEG C and 100 DEG C.
10. the preparation method of fire-retardant galapectite aerogel material according to claim 6, it is characterised in that: in step 4
In, the time for carrying out supercritical drying is 2-4h, preferably 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710418641.2A CN108997538A (en) | 2017-06-06 | 2017-06-06 | Fire-retardant galapectite aerogel material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710418641.2A CN108997538A (en) | 2017-06-06 | 2017-06-06 | Fire-retardant galapectite aerogel material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108997538A true CN108997538A (en) | 2018-12-14 |
Family
ID=64573460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710418641.2A Pending CN108997538A (en) | 2017-06-06 | 2017-06-06 | Fire-retardant galapectite aerogel material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108997538A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078973A (en) * | 2019-04-18 | 2019-08-02 | 宁波工程学院 | Phosphorous copoly type nano-meter flame retardants and preparation method thereof |
| 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999057202A2 (en) * | 1998-05-01 | 1999-11-11 | Engelhard Corporation | Low abrasion calcined kaolin pigments and enhanced filtration method |
| 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 |
| CN105854817A (en) * | 2016-03-24 | 2016-08-17 | 浙江海洋学院 | Silver-loaded nanometer titanium dioxide aerogel material used for adsorbing and degrading petroleum hydrocarbons and preparation method thereof |
| CN106244172A (en) * | 2016-07-12 | 2016-12-21 | 伊科纳诺（北京）科技发展有限公司 | A kind of preparation method of the fire-retardant aerosil of Halogen synergistic |
-
2017
- 2017-06-06 CN CN201710418641.2A patent/CN108997538A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999057202A2 (en) * | 1998-05-01 | 1999-11-11 | Engelhard Corporation | Low abrasion calcined kaolin pigments and enhanced filtration method |
| 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 |
| CN105854817A (en) * | 2016-03-24 | 2016-08-17 | 浙江海洋学院 | Silver-loaded nanometer titanium dioxide aerogel material used for adsorbing and degrading petroleum hydrocarbons and preparation method thereof |
| CN106244172A (en) * | 2016-07-12 | 2016-12-21 | 伊科纳诺（北京）科技发展有限公司 | A kind of preparation method of the fire-retardant aerosil of Halogen synergistic |
Non-Patent Citations (1)
| Title |
|---|
| HONGLI LIU: "Novel three-dimensional halloysite nanotubes/silica composite aerogels with enhanced mechanical strength and low thermal conductivity prepared at ambient pressure", 《JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078973A (en) * | 2019-04-18 | 2019-08-02 | 宁波工程学院 | Phosphorous copoly type nano-meter flame retardants and preparation method thereof |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Mechanical, thermal and flammability properties of glass fiber film/silica aerogel composites | |
| Yin et al. | Pickering emulsion: A novel template for microencapsulated phase change materials with polymer–silica hybrid shell | |
| CN111303355A (en) | Silica Janus colloidal particles and preparation method and application thereof | |
| CN107089810B (en) | A kind of aeroge modified expanded perlite insulation board and preparation method thereof | |
| CN108997538A (en) | Fire-retardant galapectite aerogel material and preparation method thereof | |
| Xian et al. | Microstructural evolution of mullite nanofibrous aerogels with different ice crystal growth inhibitors | |
| Zhang et al. | Facile synthesis of ternary flexible silica aerogels with coarsened skeleton for oil–water separation | |
| Sun et al. | High-strength and superamphiphobic chitosan-based aerogels for thermal insulation and flame retardant applications | |
| Wu et al. | Water-assisted synthesis of phenolic aerogel with superior compression and thermal insulation performance enabled by thick-united nano-structure | |
| CN109081354A (en) | Fire-retardant galapectite-silicon dioxide composite aerogel material and preparation method thereof | |
| CN108997539A (en) | Multiple dimensioned galapectite aerogel material and preparation method thereof | |
| Mingliang et al. | Thermal conductivity of silica-aerogel (SA) and autoclave aerated concrete (AAC) composites | |
| CN108997595A (en) | With mesoporous and micropore netted galapectite aerogel material and preparation method thereof | |
| CN108969467A (en) | Galapectite aerogel material and preparation method thereof | |
| CN109694539A (en) | Fire-retardant galapectite-montmorillonite Composite aerogel material and preparation method thereof | |
| CN109692632A (en) | Fire-retardant graphene-galapectite aerogel composite and preparation method thereof | |
| CN109694448A (en) | With mesoporous and micropore graphene net-galapectite aerogel composite and preparation method thereof | |
| CN109988274A (en) | With mesoporous and micropore mesh carbon nanotube-galapectite aerogel composite and preparation method thereof | |
| CN109694447A (en) | Multiple dimensioned galapectite-montmorillonite Composite aerogel material and preparation method thereof | |
| CN108976360A (en) | Three-dimensional netted galapectite aerogel material and preparation method thereof | |
| CN109081950A (en) | With mesoporous and micropore netted galapectite-silicon dioxide composite aerogel material and preparation method thereof | |
| CN110819046A (en) | Dual-network aerogel with excellent mechanical and heat-insulating properties and preparation method and application thereof | |
| CN113511877B (en) | High-strength concrete and preparation method thereof | |
| CN109010250A (en) | Galapectite-silicon dioxide composite aerogel material and preparation method thereof | |
| CN109692152A (en) | Graphene-galapectite aerogel composite 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 |
Application publication date: 20181214 |
|
| RJ01 | Rejection of invention patent application after publication |