CN109694447A - Multiple dimensioned galapectite-montmorillonite Composite aerogel material and preparation method thereof - Google Patents
Multiple dimensioned galapectite-montmorillonite Composite aerogel material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides multiple dimensioned 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 tetrabromobisphenol A, montmorillonite dispersions are prepared again, by two kinds of dispersion liquids and boric acid three (2,5-dibromos) it is added after initiator that the reaction was continued after propyl ester mixing thereto, obtain multiple dimensioned galapectite-montmorillonite Composite aerogel material.It uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilize the meso-hole structure of aeroge and the microcellular structure of fiber, load tetrabromobisphenol A and boric acid three (2 respectively, 5-dibromos) propyl ester, different characteristics fire retardant is combined, realizes cooperative flame retardant effect.
Description
Technical field
The present invention relates to technical field of nano material, more specifically to a kind of multiple dimensioned galapectite-montmorillonite Composite
Aerogel material and preparation method thereof.
Background technique
Galapectite is natural one of clay mineral, belongs to kaolinic mutation, therefore also referred to as metakaolin.It is
It is crimped under field conditions (factors) by kaolinic lamella, main existence form is nanotube-shaped (Ma Zhi, king in nature
Gold leaf, Gao Xiang, Ding Tong, application study status [J] chemical progress of Qin Yongning halloysite nanotubes, 2012, (Z1): 275-
283.).Galapectite mine is distributed in each continent in the whole world, the countries such as China, France, Belgium, New Zealand, the U.S., Turkey
There are reserves abundant.Galapectite mine is mainly distributed on Guangdong, Hubei, Hunan, Sichuan, Guizhou, Yunnan, Shanxi etc. in China and saves
Part.
Galapectite is the double-deck 1:1 type aluminosilicate material, has typical crystalline texture.Galapectite is different from kaolinic
Substantive characteristics is that galapectite interlayer exists or once there is the crystallization water, and the lamella of galapectite is the oxygen-octahedron by outer layer
It is formed with the alumina octahedral regular array of internal layer, is free hydrone among lamella.These hydrones are easy to slough, this
Dehydration is irreversible.The outer surface of galapectite is mainly Si-O-Si key composition, and inner wall is then mainly aluminium hydroxyl (Niu Ji
South, Qiang Yinghuai, Wang Chunyang, Li Xiang, Monday is great, Shang Xiangyu, name, structure, pattern and the curling mechanism of Zhuan Quanchao galapectite
[J] mineral journal, 2014, (01): 13-22.).Silicon/aluminium hydroxyl is present on the crystallization edge of galapectite or the end face of pipe,
There is a small amount of embedding hydroxyl to be present in the inside of crystalline texture.Galapectite contains the water there are three types of state, mainly absorption water, crystallization
Water and chemical water.
Halloysite nanotubes have unique nanostructure, are a kind of natural nano-materials having a extensive future.And galapectite
Nanotube is widely distributed, cheap, nontoxic.Galapectite has following because of its unique nanostructure and tubular character
Advantage: firstly, it is from a wealth of sources, it is cheap；Galapectite is a kind of natural clay mineral, contains abundant, widely distributed and exploitation
It is easier to.Secondly, having good biocompatibility；Halloysite nanotubes self-assembling formation, nontoxic, biocompatibility is preferable.
In addition, active hydroxyl groups are contained in galapectite surface and interlayer, conducive to galapectite modification and further apply.Along with itself
Have the characteristics that biggish draw ratio and specific surface area, nanoscale, galapectite has obtained extensive concern and research in recent years.
The application field of halloysite nanotubes is extensive.In ceramic material, composite material, slow-release material, catalyst carrier, mould
Plate, adsorption applications etc. have a large amount of application.Because halloysite nanotubes are a kind of clay mines, it can be used for ceramic system
Make, this belongs to traditional application field of galapectite.Galapectite has the function of fiber reinforcement, is the ideal for preparing ultra-thin fine ceramics
Raw material.In recent years, the research of galapectite/polymer composites and its performance was becoming increasingly popular.Galapectite can be
Preferably disperse in most polymer composite material, mechanical property, thermal stability, anti-flammability and the knot of polymer can be effectively improved
Brilliant performance, having biggish advantage compared with other conventional fillers, (Wu Wei, Wu Pengjun, He Ding, Cao Xianwu, Zhou Nanqiao galapectite are received
Application progress [J] chemical industry progress of the mitron in high molecule nano composite material, 2011, (12): 2647-2651+2657.).
Galapectite has the characteristics that unique texture, environmental-friendly, cheap and easy to get, can prepare tool using its design feature and characterization of adsorption
There is the material of new structure and performance, is widely used in field of nanocomposite materials.
Summary of the invention
The present invention overcomes deficiencies in the prior art, provide a kind of multiple dimensioned galapectite-montmorillonite Composite aeroge
Material and preparation method thereof uses the doughnut with microcellular structure for raw material, builds three-dimensional aeroge network, utilizes airsetting
The meso-hole structure of glue and the microcellular structure of fiber, load different flame retardant respectively, and different characteristics fire retardant is combined, and realize collaboration
Flame retardant effect.
The purpose of the present invention is achieved by following technical proposals.
Multiple dimensioned 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 tetrabromobisphenol A are added to 50 weight
In the mixed liquor of part deionized water and 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly,
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 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
It measures (2,5-dibromo) the propyl ester solution of boric acid three that part mass fraction is 0.05-18wt% to mix, be scattered in decentralized medium, to
0.01-2 parts by weight initiator is wherein added, after mixing evenly, warming-in-water to initiated polymerization at 70-90 DEG C, polymerization is instead
Between seasonable after at least 37h, place the product in CO2In supercritical high-pressure extraction device, with CO2For medium in 10-300 DEG C of temperature and
Supercritical drying at least 1h is carried out under air pressure 1-20MPa, and multiple dimensioned 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 tetrabromobisphenol A is added in the mixed solution of water and ethyl alcohol, is added to above-mentioned solution after stirring 10-60min
In galapectite dispersion liquid, ultrasonic disperse 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.
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
It measures (2,5-dibromo) the propyl ester solution of boric acid three that part mass fraction is 0.05-15wt% to mix, is scattered in 10-1000 parts by weight
In decentralized medium, 0.01-1 parts by weight initiator is added, stirs 1h, water-bath of the selection at 70-90 DEG C when carrying out polymerization reaction
Under the conditions of polymerize 12-24h in 30-50 DEG C of water bath with thermostatic control after prepolymerization 30-60min, then by it successively at 80 DEG C, 90
DEG C, it polymerize 2-8h, supercritical drying time 2-4h, preferably 3h in 100 DEG C of water bath with thermostatic control 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 tetrabromobisphenol A of middle addition are also dispersed in halloysite nanotubes hollow structure, Ai Luo
Stone nanotube hollow structure provides microcellular structure for multiple dimensioned galapectite-montmorillonite Composite aerogel material, through vacuumizing,
After washing, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed inside halloysite nanotubes and are formed crosslinking knot
Tetrabromobisphenol A is supported in halloysite nanotubes by structure, and step 3 makes be located at outside halloysite nanotubes hollow structure poly- two
It polymerize under the action of initiator between vinyl functional group on vinylsiloxane, so that halloysite nanotubes and poly-
Tridimensional network is collectively formed in divinylsiloxanes, 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 multiple dimensioned galapectite-montmorillonite Composite aerogel material, while by boric acid three
(2,5-dibromo) propyl ester 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 attached drawing 1.It can from figure
To find out, the N of the material2Adsorption-desorption curve is the IV class isothermal curve of H1 type hysteresis loop in IUPAC classification, i.e., by mesoporous
Structure generates.Illustrate that material itself has the pore structure of meso-scale.There is vertical ascent trend from the distribution of low pressure endpoint, it can be with
Sample interior is found out there are more micropore, is as caused by absorption potential strong inside micropore.By nitrogen adsorption desorption isotherm number
According to the sample specific surface area can reach 602.14m2g-1, which exists simultaneously mesoporous-micropore second level pore structure, through more
The average specific surface area of group measurement material is 600-605m2g-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=-0.913/ln (p/p0), unit nm, while adding adsorbent layer thickness t=0.367 [- 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
10.32nm, another kind are 2.49 μm, are measured through multiple groups, and nanoscale hole is average up to 10-11nm, and micro-meter scale hole is flat
Up to 2-4 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 multiple dimensioned galapectite-montmorillonite Composite aerogel material N2Adsorption-desorption curve；
Fig. 2 is multiple dimensioned 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 4000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 0.8%), 0.6g azodiisobutyronitrile (ABIN),
0.3g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 13min, is added to galapectite dispersion
In liquid, ultrasonic disperse 20min keeps 0.5h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats vacuum step
It after three times, after product is washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 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
(2,5-dibromo) the propyl ester solution of boric acid three that score is 10wt% mixes, and is scattered in 1000g decentralized medium, and it is even that 0.01g is added
Nitrogen bis-isobutyronitrile (ABIN), 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, 0.3g poly- divinylsiloxanes (number-average molecular weight 3200, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of mole percent 1.5%), 1g dibenzoyl peroxide (BPO),
0.5g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 24min, is added to galapectite dispersion
In liquid, ultrasonic disperse 35min keeps 2h after vacuumizing above-mentioned mixed liquor, is 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
(2,5-dibromo) the propyl ester solution of boric acid three that number is 0.65wt% mixes, and is scattered in 10g decentralized medium, and 0.3g peroxide is added
Change dibenzoyl (BPO), stirring 1h is placed on prepolymerization 60min under 70 DEG C of water bath condition, then in 30 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 23h
It is placed 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,
The multiple dimensioned carrier aeroge of galapectite/montmorillonite can be obtained.
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, 0.4g poly- divinylsiloxanes (number-average molecular weight 2400, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino list sealing end of mole percent 2.5%), 0.44g dibenzoyl peroxide
(BPO), 5g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 34min, is added to galapectite
In dispersion liquid, ultrasonic disperse 32min keeps 1h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, and repetition vacuumizes step
Suddenly three times after, after product is washed, be scattered in 100g water, be placed under 75 DEG C of water bath condition after prepolymerization 60min at 50 DEG C
Water bath with thermostatic control in polymerize 20 hours, after it is successively then polymerize 6h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control,
It after product is washed, is scattered in 100g water, obtains dispersion liquid A；5h is dried into 2.6g montmorillonite at 95 DEG C, then is matched with solvent
It is set to the montmorillonite dispersions that mass fraction is 8wt%；By montmorillonite dispersions with the speed mechanical of 400r/min at 25 DEG C
8h is stirred, then with the ultrasonic treatment 6h of 120W power, obtains dispersion liquid B；By 6g dispersion liquid A, 3g dispersion liquid B, 0.5g mass point
(2,5-dibromo) the propyl ester solution of boric acid three that number is 0.05wt% mixes, and is scattered in 562g decentralized medium, and 0.9g peroxide is added
Change dibenzoyl (BPO), stirring 1h is placed on prepolymerization 55min under 71 DEG C of water bath condition, then 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 product by middle polymerization 90h
It is placed in CO2In supercritical high-pressure extraction device, with CO2Supercritical drying is carried out at 16 DEG C of temperature and air pressure 15MPa for medium
The multiple dimensioned carrier aeroge of galapectite/montmorillonite can be obtained in 3h.
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 bi-end-blocking of mole percent 0.1%), 0.01g azodiisobutyronitrile (ABIN),
0.22g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, stirs 60min, is added to galapectite dispersion
In liquid, ultrasonic disperse 34min keeps 0.5h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, repeats vacuum step
It after three times, after product is washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 55min at 50 DEG C
It polymerize 12 hours in water bath with thermostatic control, it, will after it is successively then polymerize 2h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
After product washing, it is scattered in 100g water, obtains dispersion liquid A；6h is dried into 0.1g montmorillonite at 144 DEG C, then is matched with solvent
It is set to the montmorillonite dispersions that mass fraction is 4.6wt%；By montmorillonite dispersions at 5 DEG C with the speed mechanical of 256r/min
10h is stirred, then with the ultrasonic treatment 15h of 260W power, obtains dispersion liquid B；By 5.3g dispersion liquid A, 1g dispersion liquid B, 0.89g matter
It measures (2,5-dibromo) the propyl ester solution of boric acid three that score is 15wt% to mix, is scattered in 352g decentralized medium, 0.06g is added
Azodiisobutyronitrile (ABIN), stirring 1h is placed on prepolymerization 53min under 90 DEG C of water bath condition, then in 50 DEG C of thermostatted water
It polymerize 16h in bath, 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, will be produced
Object is placed in CO2In supercritical high-pressure extraction device, with CO2Supercritical drying is carried out at 300 DEG C of temperature and air pressure 20MPa for medium
The multiple dimensioned carrier aeroge of galapectite/montmorillonite can be obtained in 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, (number-average molecular weight 500, contents of ethylene rubs the poly- divinylsiloxanes of 0.7g
The poly dimethyl divinylsiloxanes of the amino list sealing end of your percentage 5%), 0.7g azodiisobutyronitrile (ABIN), 0.1g
Tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 29min, is added in galapectite dispersion liquid,
Ultrasonic disperse 28min keeps 1h after vacuumizing above-mentioned mixed liquor, be then restored to normal pressure, after repeating vacuum step three times,
It after product is washed, is scattered in 100g water, is placed under 75 DEG C of water bath condition after prepolymerization 31min in 50 DEG C of water bath with thermostatic control
Middle polymerization 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, product is washed
Afterwards, it is scattered in 100g water, obtains dispersion liquid A；18h is dried into 6.5g montmorillonite at 120 DEG C, then is configured to quality with solvent
Score is the montmorillonite dispersions of 18wt%；Montmorillonite dispersions are stirred into 3h at 35 DEG C with the speed mechanical of 332r/min,
The ultrasonic treatment 8h for using 250W power again, obtains dispersion liquid B；It is by 10g dispersion liquid A, 9g dispersion liquid B, 15g mass fraction
(2,5-dibromo) the propyl ester solution of boric acid three of 5.2wt% mixes, and is scattered in 152g decentralized medium, and two isobutyl of 1g azo is added
Nitrile (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 2000, contents of ethylene rubs the poly- divinylsiloxanes of 1g
The poly dimethyl divinylsiloxanes of the amino list sealing end of your percentage 3%), 0.5g dibenzoyl peroxide (BPO), 3.5g
Tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 10min, is added in galapectite dispersion liquid,
Ultrasonic disperse 24min keeps 1.5h 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 30min in 50 DEG C of constant temperature
It polymerize in water-bath 21 hours, after it is successively then distinguished polyase 13 h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control, by product
It after washing, is scattered in 100g water, obtains dispersion liquid A；15h is dried into 3g montmorillonite at 66 DEG C, then is configured to matter with solvent
Measure the montmorillonite dispersions that score is 0.5wt%；Montmorillonite dispersions are stirred at 6 DEG C with the speed mechanical of 150r/min
9h, then with the ultrasonic treatment 12h of 50W power, obtain dispersion liquid B；It is by 9g dispersion liquid A, 30g dispersion liquid B, 2.6g mass fraction
(2,5-dibromo) the propyl ester solution of boric acid three of 13wt% mixes, and is scattered in 998g decentralized medium, and 0.65g peroxidating two is added
Benzoyl (BPO), stirring 1h are placed on prepolymerization 44min under 85 DEG C of water bath condition, then gather in 35 DEG C of water bath with thermostatic control
28h 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 10 DEG C of temperature and air pressure 10MPa for medium, it can
Obtain the multiple dimensioned carrier aeroge of galapectite/montmorillonite.
Embodiment 7
12g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
Galapectite dispersion liquid, by 12g sodium styrene sulfonate, 1.6g poly- divinylsiloxanes (number-average molecular weight 3000, contents of ethylene
The poly dimethyl divinylsiloxanes of the amino bi-end-blocking of mole percent 1.5%), 0.3g azodiisobutyronitrile (ABIN),
8g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 13min, is added to galapectite dispersion liquid
In, ultrasonic disperse 30min 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 70 DEG C of water bath condition after prepolymerization 56min in 40 DEG C of constant temperature
It polymerize 15 hours in water-bath, after it is successively then polymerize 5h 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；11h is dried into 12g montmorillonite at 180 DEG C, then is configured to solvent
Mass fraction is the montmorillonite dispersions of 24wt%；Montmorillonite dispersions are stirred at 30 DEG C with the speed mechanical of 165r/min
4h, then with the ultrasonic treatment 14h of 226W power, obtain dispersion liquid B；By 12g dispersion liquid A, 32g dispersion liquid B, 18g mass fraction
It mixes, is scattered in 1000g decentralized medium for (2,5-dibromo) the propyl ester solution of boric acid three of 18wt%, 1.2g azo two is added
Isobutyronitrile (ABIN), stirring 1h are placed on prepolymerization 39min under 88 DEG C of water bath condition, then gather in 42 DEG C of water bath with thermostatic control
19h 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 4h is carried out at 10 DEG C of temperature and air pressure 20MPa for medium, it can
Obtain the multiple dimensioned carrier aeroge of galapectite/montmorillonite.
Embodiment 8
0.7g halloysite nanotubes are added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, ultrasonic disperse 1h is obtained
To galapectite dispersion liquid, by 0.7g sodium styrene sulfonate, 0.06g poly- divinylsiloxanes (number-average molecular weight 1000, vinyl
The poly dimethyl divinylsiloxanes of the amino list sealing end of content mole percent 4%), 0.01g dibenzoyl peroxide
(BPO), 0.08g tetrabromobisphenol A is added in the mixed liquor of 50g deionized water and 50g ethyl alcohol, is stirred 60min, is added to Ai Luo
In stone dispersion liquid, ultrasonic disperse 22min keeps 2h after vacuumizing above-mentioned mixed liquor, is then restored to normal pressure, and repetition vacuumizes
Step three times after, after product is washed, be scattered in 100g water, be placed under 80 DEG C of water bath condition after prepolymerization 55min 60
DEG C water bath with thermostatic control in polymerize 12 hours, it is successively then polymerize 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control respectively
Afterwards, it after product being washed, is scattered in 100g water, obtains dispersion liquid A；6h is dried into 0.08g montmorillonite at 144 DEG C, then is used
Solvent is configured to the montmorillonite dispersions that mass fraction is 0.08wt%；By montmorillonite dispersions at 5 DEG C with 256r/min's
Speed mechanical stirs 10h, then with the ultrasonic treatment 15h of 260W power, obtains dispersion liquid B；0.8g dispersion liquid A, 0.7g are dispersed
(2,5-dibromo) the propyl ester solution of boric acid three that liquid B, 0.4g mass fraction is 0.05wt% mixes, and is scattered in 352g decentralized medium
In, it is added 0.01g dibenzoyl peroxide (BPO), stirring 1h is placed on prepolymerization 53min under 90 DEG C of water bath condition, then
It polymerize 16h in 50 DEG C of water bath with thermostatic control, after it is successively respectively then placed 2h in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control
Obtained solution, place the product in CO2In supercritical high-pressure extraction device, with CO2It is medium at 270 DEG C of temperature and air pressure 18MPa
Supercritical drying 2h is carried out, the multiple dimensioned carrier aeroge of galapectite/montmorillonite can be obtained.
Flame retardant property test:
The material and EVA (mass ratio 1:4) for taking the method for the invention to prepare, are warming up to 140 DEG C for mixer, 45
EVA is added under conditions of rev/min, the material of invention the method preparation is added after constant torque, keeps 10min to mixing
Uniformly.Composite material after mixing is put into vulcanizing press, sample processed is molded with 140 DEG C of 10MPa, is placed on dry and ventilated
Place is for 24 hours.According to GB/T2406.2-2009, GB8624-2006 and document (Li Bin, Wang Jianqi, polymer material flammability and resistance
Evaluation --- cone calorimetry (CONE) method of combustion property, polymer material science and engineering, 1998,14:15) the method measurement
Composite material limit oxygen index, maximum heatrelease rate and ignitor firing time, the results are shown in Table 1.
The flame retardant property of 1 material of table
| Embodiment | Limit oxygen index (%) | Maximum heatrelease rate (kW/m2) | Ignitor firing time (s) |
| Blank | 18 | 722 | 95 |
| Embodiment 1 | 79 | 233 | 218 |
| Embodiment 2 | 95 | 221 | 220 |
| Embodiment 3 | 83 | 208 | 221 |
| Embodiment 4 | 76 | 230 | 237 |
| Embodiment 5 | 95 | 225 | 249 |
| Embodiment 6 | 99 | 220 | 218 |
| Embodiment 7 | 85 | 210 | 232 |
| Embodiment 8 | 93 | 215 | 229 |
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. multiple dimensioned galapectite-montmorillonite Composite aerogel material, it is characterised in that: galapectite-montmorillonite Composite airsetting glue material
Material average specific surface area is 600-605m2g-1, nanoscale and micro- is existed simultaneously in galapectite-montmorillonite Composite aerogel material
Metrical scale hole, nanoscale hole average out to 10-11nm, 2-4 μm of average out to of micro-meter scale hole, as steps described below into
Row:
Step 1,0.7-12 parts by weight halloysite nanotubes are added to the mixed of 50 parts by weight of deionized water and 50 parts by weight of ethanol
It closes in liquid, ultrasonic disperse is uniform, galapectite dispersion liquid is obtained, by 0.7-12 parts by weight of styrene sodium sulfonate, 0.06-1.6 weight
The poly- divinylsiloxanes of part, 0.01-0.3 parts by weight initiator, 0.08-8 parts by weight tetrabromobisphenol A are added to 50 parts by weight and go
In ionized water and the mixed liquor of 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, ultrasound
After being uniformly dispersed, vacuum is kept after vacuumizing, and is then restored to normal pressure, after repeating vacuum step three times, after product is washed,
It is scattered in 100 parts by weight water, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization reaction time at least 50h, washs
It is dispersed in 100 parts by weight water, obtains the dispersion liquid of step 1；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole 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
(2,5-dibromo) the propyl ester solution of boric acid three that mass fraction is 0.05-18wt% mixes, and is 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 multiple dimensioned galapectite-montmorillonite Composite aerogel material can be obtained.
2. multiple dimensioned 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 tetrabromo
Bisphenol-A is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added in galapectite dispersion liquid after stirring 10-60min,
Ultrasonic disperse 20-35min keeps vacuum 0.5-2h, water-bath item of the selection at 70-80 DEG C when carrying out polymerization reaction after vacuumizing
It polymerize 12-24h under part after prepolymerization 30-60min in 40-60 DEG C of water bath with thermostatic control, then by it successively at 80 DEG C, 90 DEG C,
It polymerize 2-8h respectively in 100 DEG C of water bath with thermostatic control.
3. multiple dimensioned 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. multiple dimensioned 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
(2,5-dibromo) the propyl ester solution of boric acid three of 0.05-15wt% mixes, and is scattered in 10-1000 parts by weight decentralized medium, is 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. multiple dimensioned galapectite-montmorillonite Composite aerogel material according to claim 1, it is characterised in that: initiator
Select dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
6. multiple dimensioned galapectite-montmorillonite Composite aerogel material preparation method, it is characterised in that: as steps described below into
Row:
Step 1,0.7-12 parts by weight halloysite nanotubes are added to the mixed of 50 parts by weight of deionized water and 50 parts by weight of ethanol
It closes in liquid, ultrasonic disperse is uniform, galapectite dispersion liquid is obtained, by 0.7-12 parts by weight of styrene sodium sulfonate, 0.06-1.6 weight
The poly- divinylsiloxanes of part, 0.01-0.3 parts by weight initiator, 0.08-8 parts by weight tetrabromobisphenol A are added to 50 parts by weight and go
In ionized water and the mixed liquor of 50 parts by weight of ethanol, above-mentioned solution is added in galapectite dispersion liquid after mixing evenly, ultrasound
After being uniformly dispersed, vacuum is kept after vacuumizing, and is then restored to normal pressure, after repeating vacuum step three times, after product is washed,
It is scattered in 100 parts by weight water, warming-in-water to initiated polymerization at 70-80 DEG C, polymerization reaction time at least 50h, washs
It is dispersed in 100 parts by weight water, obtains the dispersion liquid of step 1；
Poly- divinylsiloxanes be number-average molecular weight 500-5000, preferably 1000-3000, contents of ethylene mole 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
(2,5-dibromo) the propyl ester solution of boric acid three that mass fraction is 0.05-18wt% mixes, and is 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 multiple dimensioned 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 tetrabromobisphenol A entered is also dispersed in halloysite nanotubes hollow structure, and galapectite is received
Mitron hollow structure provides microcellular structure for multiple dimensioned galapectite-montmorillonite Composite aerogel material, by vacuumizing, washing
Afterwards, poly- divinylsiloxanes are copolymerized with sodium styrene sulfonate, are formed and are formed cross-linked structure inside halloysite nanotubes, will
Tetrabromobisphenol A is supported in halloysite nanotubes, and step 3 makes the poly- divinyl being located at outside halloysite nanotubes hollow structure
It polymerize under the action of initiator between vinyl functional group on siloxanes, so that halloysite nanotubes and poly- divinyl
Radical siloxane is collectively formed tridimensional network, and the montmorillonite being added in step 2 is successfully configured to network pore structure, and above-mentioned three
Dimension reticular structure and montmorillonite are successfully configured to network pore structure and together form three-dimensional network pore structure, above-mentioned three dimensional network
Network pore structure provides meso-hole structure for multiple dimensioned galapectite-montmorillonite Composite aerogel material, while by boric acid three (2,5-
Dibromo) propyl ester is supported in meso-hole structure.
7. the preparation method of multiple dimensioned 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 tetrabromobisphenol A is added in the mixed solution of water and ethyl alcohol, and above-mentioned solution is added to Ai Luo after stirring 10-60min
In stone dispersion liquid, ultrasonic disperse 20-35min keeps vacuum 0.5-2h after vacuumizing, when carrying out polymerization reaction, selection is in 70-
It polymerize 12-24h in 40-60 DEG C of water bath with thermostatic control after prepolymerization 30-60min under 80 DEG C of water bath condition, then successively by it
It polymerize 2-8h respectively in 80 DEG C, 90 DEG C, 100 DEG C of water bath with thermostatic control.
8. the preparation method of multiple dimensioned 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 multiple dimensioned 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
(2,5-dibromo) the propyl ester solution of boric acid three that mass fraction is 0.05-15wt% mixes, and is scattered in the dispersion of 10-1000 parts by weight
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.
10. the preparation method of multiple dimensioned galapectite-montmorillonite Composite aerogel material according to claim 6, feature
Be: initiator selects dibenzoyl peroxide (BPO) or azodiisobutyronitrile (ABIN).
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| 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 |
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Application publication date: 20190430 |