CN107778875A - Polysilazane zirconium dioxide aerogel composite and its preparation method and application - Google Patents
Polysilazane zirconium dioxide aerogel composite and its preparation method and application Download PDFInfo
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
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Abstract
The present invention discloses polysilazane zirconium dioxide aerogel composite and its preparation method and application, polysilazane precursor is scattered in toluene, sequentially add tetrabutyl zirconate and divinylbenzene, it is uniformly mixing to obtain mixing weak solution rapidly, mixing weak solution is transferred in hydrothermal reaction kettle and sealed, the reactor for filling mixing weak solution is placed in drying box and reacted, is cooled to room temperature, wet gel is obtained, wet gel is put into the beaker for fill toluene and stood；Step 1 product is transferred in carbon dioxide supercritical extraction device, impregnated in liquid carbon dioxide, supercritical drying, that is, obtains polysilazane zirconium dioxide aerogel composite.Polysilazane-zirconium dioxide aerogel composite of the present invention is composite porous for a kind of novel nano, has very high porosity, specific surface area, low-density；Preparation condition is gentle, technique is simple, controllable.
Description
Technical field
The present invention relates to a kind of precursor polysilazane-zirconium dioxide aerogel composite and preparation method thereof, belong to
The preparation technology field of nano-porous materials.
Background technology
Aeroge is mutually coalesced the one kind with tridimensional network formed by nano-particle or high-polymer molecular and consolidated
Body nanoporous materials, it be by wet gel maintain its hole and spacial framework it is not destroyed and by its space
Liquid air substitute after obtained by product.Aeroge is the minimum solid material of current world's upper density and thermal conductivity,
Density can as little as 0.0029g/m3, room temperature in vacuo thermal conductivity can reach 0.001W/mK.The special structure of aeroge makes it have simultaneously
Advantage of both standby lightweight and effectively insulating, can be widely applied to the fields such as heat, light, sound, electricity, mechanics, by scientific research circle with
The extensive concern of industrial quarters, it is described as one of material of 21st century most development potentiality.Since being born from aeroge, grind
The most mainly SiO studied carefully2Aeroge and C aeroges.But SiO2, C aeroges there is high temperature limitation in itself.Polysilazane
The SiCN ceramics that precursor is prepared by precursor pyrolysis and hot pressing belong to anaerobic ceramics, have good heat endurance, creep, oxygen
The temperature changed, crystallize, be separated can reach 1400 DEG C, significantly larger than SiO2, C aeroges, but study find polysilazane ceramics
Si present in preceramic polymer thermal decomposition product3N4Ceramics start to crystallize at 1400 DEG C or so substantially, cause material to become fragile, body
Free carbon present in system can also accelerate it in N21480 DEG C or so of decomposition reaction in atmosphere.So in polysilazane precursor
It is middle to introduce the transition metals such as a small amount of boron and zirconium, titanium, chromium, the resistance to elevated temperatures of thermal decomposition product can be significantly increased.Mesh
It is preceding on preparing the zirconium dioxide composite aerogel of precursor polysilazane one by silicon source of precursor polysilazane (PSN) polymer
Report it is fresh few.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of precursor polysilazane-zirconium dioxide is multiple
Close aerogel material and preparation method thereof.Using sol-gal process and supercritical drying process, prepare pattern and aperture is controllable
Ceramic aerogel.
The purpose of the present invention is achieved by following technical proposals.
Polysilazane-zirconium dioxide aerogel composite and preparation method thereof, is followed the steps below：
Step 1, polysilazane precursor is scattered in toluene, sequentially adds tetrabutyl zirconate and divinylbenzene, it is fast
Speed is uniformly mixing to obtain mixing weak solution, and above-mentioned mixing weak solution is transferred in hydrothermal reaction kettle and sealed, will fill mixing
The reactor of weak solution is placed in 160-200 DEG C of drying box after reaction 1-6h, is cooled to 20-25 DEG C of room temperature, is obtained wet gel, will
Above-mentioned wet gel is put into the beaker for filling toluene, stands 24-36h；
Step 2, step 1 product is transferred in carbon dioxide supercritical extraction device, impregnated in liquid carbon dioxide
0.5-2.0h, after then carrying out supercritical drying, that is, obtain polysilazane-zirconium dioxide aerogel composite.
The density of the polysilazane-zirconium dioxide aerogel composite prepared according to the above method is 0.04-0.10 g/
cm3, porosity 90-98%, specific surface area is 400-600 m2g-1, water contact angle is 160-170 °, and thermal conductivity factor averagely may be used
Up to 0.015-0.025W/mK.
In step 1, polysilazane precursor be 4-10 parts by weight, the toluene of scattered polysilazane precursor be 4-10
Parts by weight, tetrabutyl zirconate are 0.5-2.5 parts by weight, divinylbenzene is 4-8 parts by weight, and preferably polysilazane precursor is
5-8 parts by weight, the toluene of scattered polysilazane precursor are 5-8 parts by weight, tetrabutyl zirconate is 1-2 parts by weight, divinyl
Base benzene is 5-6 parts by weight.
In step 1, the reactor for filling mixing weak solution reacts 2-5h in 180-200 DEG C of drying box.
In step 1, wet gel is put into beaker, is submerged wet gel with toluene, is stood 25-30 hours.
In step 1, polysilazane is linear structure, and main chain is formed by Si, N atom are alternate, there is Si -- H bond in structure, and
There is vinyl sidechain, its molal weight is 800-1500g/mol, preferably 1000-1200g/mol, shown in following molecular formula.
In step 2, step 1 product dip time in liquid carbon dioxide is 1-1.5h.
In step 2, the condition of supercritical drying is：Drying temperature be 40-50 DEG C, preferably 45-48 DEG C, drying pressure
For 5-10MPa, preferably 8-10MPa, preferably drying time 5-9h, 6-8h.
The present invention utilizes CO 2 supercritical high pressure extraction experimental provision (200mL), with liquid carbon dioxide to wet solidifying
Glue carries out supercritical drying, i.e., the solvent adsorbed with liquid carbon dioxide to wet gel enters line replacement, and keeps gel simultaneously
Network structure.The outward appearance of composite aerogel still keeps the original shape of aeroge, as shown in figure 1, being advantageous to composite aerogel holding
Its original porosity etc..Adsorbent of the composite of the present invention as organic dyestuff in wastewater.
The present invention is by the use of polysilazane and tetrabutyl zirconate as precursor, and divinylbenzene is as crosslinking agent, by poly-
The Si -- H bond of silazane and the vinyl (- CH=CH of divinylbenzene2) between hydrosilylation prepare ZrO2It is dispersed
In the composite aerogel of system, this hydrosilylation based on liquid-liquid dispersion system ensure that the bone of final composite aerogel
ZrO in frame2Nano-particle is uniformly distributed, so as to avoid the occurrence of the dispersion problem as caused by gravity, through Bei Shide instruments section
N2 adsorption specific surface area measuring instrument (3H-2000PS1) measure of skill (Beijing) Co., Ltd, the aeroge prepared by the present invention are answered
The porosity of condensation material can reach more than 90%, even aperture distribution, be 2-100nm mesoporous materials, as shown in Figure 2.
Determined using the FTISs of Thermo companies of U.S. Nicolet 380 poly- before participating in reaction
The infrared spectrum of silazane and composite aerogel, as shown in Figure 3.Wherein curve (a) is the infrared curve of polysilazane, and (b) is
The infrared curve of polysilazane-titanium dioxide composite aerogel.In Fig. 3 (a) spectrogram, 2100cm-1Place has Si -- H bond to stretch
Vibration absorption peak, in 1265cm-1There are Si-C absworption peaks position.In Fig. 3 (b) spectrogram, Zr-O-Zr skeletal vibration absworption peak
Positioned at 1461cm-1Near；2100cm-1Place's Si-H vibration peaks substantially weaken, and in 1200cm-1Nearby newly there are C-C saturated bonds
Absworption peak, and in 1580cm-1Newly there are aromatic hydrocarbon C=C key chattering absworption peaks in place.Result above has absolutely proved poly- silicon nitrogen
The Si -- H bond of alkane and the vinyl (- CH=CH of divinylbenzene2) between hydrosilylation occurs.
The microscopic appearance of composite aerogel sample is observed using JEOL JSM-7800F types SEM,
As shown in figure 4, the aeroge has the three-dimensional net structure of even aperture distribution.Adsorbed as shown in Figure 5 for composite aerogel
The performance test of methylene blue, composite aerogel is added in the MB solution that initial concentration is 10mg/L, show composite aerogel
There is good absorption property to methylene blue MB, MB in the aqueous solution can be rapidly removed, (increased to as soak time increases
30min), aqueous solution Methylene Blue concentration is gradually reduced, and can be confirmed from picture and ultraviolet spectra.Simultaneously as
Composite aerogel has good heat endurance under high temperature, and composite aerogel can be by calcining in atmosphere after adsorbing organic dyestuff
Remove MB and be recycled.Therefore, composite aerogel may be used as excellent adsorbent and be synthesized with removing from the aqueous solution
Dyestuff, i.e. the application of polysilazane-titanium dioxide aerogel composite of the invention in synthetic dyestuffs in removing the aqueous solution,
Such as methylene blue.
Macroscopical hydrophobic performance of sample is characterized using contact angle measurement, using the German limited public affairs of Dataphysics instruments
Department's OCA20 contact angles system is tested the contact angle of the aeroge of polycarbosilane precusor containing zirconium at room temperature：With micro
SNS021/011 pins drip to 4 microlitres of ultrapure water droplets on aeroge sample to be measured, test sample to be tested contact angle, as shown in fig. 6,
The water contact angle of the aeroge is that 161 ° and aeroge test block can float on the water surface and nonwetting, shows that composite aerogel has
Ultra-hydrophobicity.
It is that a kind of novel nano is porous by polysilazane-ZrO_2 aerogel prepared by the technological approaches of the present invention
Composite, there is very high porosity, specific surface area, low-density, the field such as absorption, waterproof, heat-insulated can be widely used in,
Using the method preparation condition is gentle, technique is simple, controllable.
Brief description of the drawings
Fig. 1 is the photo in kind of polysilazane-ZrO_2 aerogel composite.
Fig. 2 is nitrogen adsorption-desorption curve figure (a) and the aperture point of polysilazane-ZrO_2 aerogel composite
Cloth curve map (b).
Fig. 3 is the FT-IR spectrograms of polysilazane-ZrO_2 aerogel composite, wherein, (a) is polysilazane
Infrared curve, (b) are the infrared curve of polysilazane-zirconium dioxide composite aerogel.
Fig. 4 is the SEM photograph of polysilazane-ZrO_2 aerogel composite.
Fig. 5 is the UV-VIS absorption spectrums of polysilazane-ZrO_2 aerogel composite absorption methylene blue.
Fig. 6 is the hydrophobicity photo of polysilazane-ZrO_2 aerogel composite.
Embodiment
Technical scheme is further described below by specific embodiment.
Wherein, the polysilazane precursor containing vinyl sidechain is purchased from Chemistry In China research institute, and its relative molecular weight is
1000g/mol, molecular structural formula see below shown, x in formula, y, and z is integer, and the main chain of the precursor is alternately bonded by Si, N key
, active group Si-H and-CH is contained in molecular structure2=CH2- side chain；Tetrabutyl zirconate is purchased from Shanghai Aladdin biochemical technology
Limited company；Other reagents and raw material are purchased from Tianjin Ke Wei Co., Ltds；What supercritical drying experimental provision used
It is Nantong Huaan Overcritical Extraction Co., Ltd.；Porosity and density measurement are using scientific and technological (Beijing) the limited public affairs of Bei Shide instruments
The N2 adsorption specific surface area measuring instrument of department.
Embodiment 1
Step (1) is by polysilazane (PSN) pioneer containing vinyl sidechain, Si -- H bond of 0.40g number-average molecular weights 1000
Body is scattered in 0.40g toluene, is sequentially added 0.05g tetrabutyl zirconates (TBT) and 0.50g divinylbenzenes (DVB), is stirred rapidly
Mix uniformly, then the mixing weak solution being configured to is transferred in the polytetrafluoroethyllining lining of hydrothermal reaction kettle, seal；It will fill
The reactor of mixed liquor, which is placed in 180 DEG C of drying boxes, reacts 3h, to be cooled to arrive room temperature, obtains wet gel, and toluene is added and filled
To submergence wet gel test block in the beaker of wet gel, it is stand-by to stand 24h.
Product in step (1) is transferred in carbon dioxide supercritical extraction device by step (2), in liquid carbon dioxide
About 1h is impregnated, is respectively then 45 DEG C and progress supercritical drying 6h under 8MPa in drying temperature and pressure.
The specific surface area, porosity and density of desciccate are tested, the results are shown in Table 1.
Embodiment 2
Step (1) is by polysilazane (PSN) pioneer containing vinyl sidechain, Si -- H bond of 0.40g number-average molecular weights 1000
Body is scattered in 0.40g toluene, is sequentially added 0.10g tetrabutyl zirconates (TBT) and 0.60g divinylbenzenes (DVB), is stirred rapidly
Mix uniformly, then the mixing weak solution being configured to is transferred in the polytetrafluoroethyllining lining of hydrothermal reaction kettle, seal；It will fill
The reactor of mixed liquor, which is placed in 160 DEG C of drying boxes, reacts 6h, to be cooled to arrive room temperature, obtains wet gel, and toluene is added and filled
To submergence wet gel test block in the beaker of wet gel, it is stand-by to stand 36h.
Product in step (1) is transferred in carbon dioxide supercritical extraction device by step (2), in liquid carbon dioxide
About 0.5h is impregnated, is respectively then 40 DEG C and progress supercritical drying 7h under 9MPa in drying temperature and pressure.
The specific surface area, porosity and density of desciccate are tested, the results are shown in Table 1.
Embodiment 3
Step (1) is by polysilazane (PSN) pioneer containing vinyl sidechain, Si -- H bond of 0.40g number-average molecular weights 1000
Body is scattered in 0.40g toluene, is sequentially added 0.20g tetrabutyl zirconates (TBT) and 0.80g divinylbenzenes (DVB), is stirred rapidly
Mix uniformly, then the mixing weak solution being configured to is transferred in the polytetrafluoroethyllining lining of hydrothermal reaction kettle, seal；It will fill
The reactor of mixed liquor, which is placed in 200 DEG C of drying boxes, reacts 1h, to be cooled to arrive room temperature, obtains wet gel, and toluene is added and filled
To submergence wet gel test block in the beaker of wet gel, it is stand-by to stand 32h.
Product in step (1) is transferred in carbon dioxide supercritical extraction device by step (2), in liquid carbon dioxide
About 2h is impregnated, is respectively then 50 DEG C and progress supercritical drying 8h under 7MPa in drying temperature and pressure.
The specific surface area, porosity and density of desciccate are tested, the results are shown in Table 1.
Embodiment 4
Step (1) is by polysilazane (PSN) pioneer containing vinyl sidechain, Si -- H bond of 0.40g number-average molecular weights 1000
Body is scattered in 0.40g toluene, is sequentially added 0.15g tetrabutyl zirconates (TBT) and 0.70g divinylbenzenes (DVB), is stirred rapidly
Mix uniformly, then the mixing weak solution being configured to is transferred in the polytetrafluoroethyllining lining of hydrothermal reaction kettle, seal；It will fill
The reactor of mixed liquor, which is placed in 170 DEG C of drying boxes, reacts 5h, to be cooled to arrive room temperature, obtains wet gel, incites somebody to action, toluene is added and filled
To submergence wet gel test block in the beaker of wet gel, it is stand-by to stand 30h.
Product in step (1) is transferred in carbon dioxide supercritical extraction device by step (2), in liquid carbon dioxide
About 1.5h is impregnated, is respectively then 45 DEG C and progress supercritical drying 9h under 8MPa in drying temperature and pressure.
The specific surface area, porosity and density of desciccate are tested, the results are shown in Table 1.
The performance of 1 polysilazane of table-ZrO_2 aerogel composite
| Embodiment | Density (g/cm3) | Porosity (%) | Specific surface area (m2g-1) |
| 1 | 0.0981 | 91 | 451.3480 |
| 2 | 0.0872 | 92 | 513.9441 |
| 3 | 0.0436 | 96 | 547.6579 |
| 4 | 0.0654 | 94 | 532.5414 |
The preparation technology of aeroge is adjusted according to foregoing invention content, the aerogel products finally prepared show with embodiment
Go out essentially identical property.On average, density 0.04-0.10g/cm3, porosity 90-98%, specific surface area 400-
600m2g-1, water contact angle is 160-170 °；Use Xi'an Xiatech Electronic Technology Co., Ltd. TC3000E type thermal conductivity factors simultaneously
Instrument carries out the test of thermal conductivity factor to the aerogel products of preparation, and thermal conductivity factor is average up to 0.015-0.025W/mK.
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. polysilazane-zirconium dioxide aerogel composite, it is characterised in that follow the steps below：
Step 1, polysilazane precursor is scattered in toluene, sequentially adds tetrabutyl zirconate and divinylbenzene, stir rapidly
Mix and uniformly obtain mixing weak solution, above-mentioned mixing weak solution is transferred in hydrothermal reaction kettle and sealed, it is dilute molten that mixing will be filled
The reactor of liquid is placed in 160-200 DEG C of drying box after reaction 1-6h, is cooled to 20-25 DEG C of room temperature, is obtained wet gel, by described in
Wet gel is put into the beaker for filling toluene, stands 24-36h；
Step 2, step 1 product is transferred in carbon dioxide supercritical extraction device, 0.5- is impregnated in liquid carbon dioxide
2.0h, after then carrying out supercritical drying, that is, obtain polysilazane-zirconium dioxide aerogel composite；
The density of polysilazane-zirconium dioxide aerogel composite is 0.04-0.10g/cm3, porosity 90-98%, compare table
Area is 400-600m2g-1, water contact angle is 160-170 °, and thermal conductivity factor is average up to 0.015-0.025W/mK；Aperture point
Cloth is uniform, is 2-100nm mesoporous materials；
In step 1, polysilazane precursor be 4-10 parts by weight, the toluene of scattered polysilazane precursor be 4-10 weight
Part, tetrabutyl zirconate are 0.5-2.5 parts by weight, divinylbenzene is 4-8 parts by weight；Polysilazane is linear structure, main chain by
Si, N atom are alternate to be formed, and has Si -- H bond in structure, and has vinyl sidechain, and its molal weight is 800-1500g/mol；
In step 2, the condition of supercritical drying is：Drying temperature is 40-50 DEG C, drying pressure 5-10MPa, drying time 5-
9h。
2. polysilazane according to claim 1-zirconium dioxide aerogel composite, it is characterised in that in step 1
In, polysilazane precursor is 5-8 parts by weight, the toluene of scattered polysilazane precursor is 5-8 parts by weight, tetrabutyl zirconate
It is 5-6 parts by weight for 1-2 parts by weight, divinylbenzene, the molal weight of polysilazane is 1000-1200g/mol.
3. polysilazane according to claim 1-zirconium dioxide aerogel composite, it is characterised in that in step 1
In, the reactor for filling mixing weak solution reacts 2-5h in 180-200 DEG C of drying box；Wet gel is put into beaker,
Wet gel is submerged with toluene, stands 25-30 hours.
4. polysilazane according to claim 1-zirconium dioxide aerogel composite, it is characterised in that in step 2
In, step 1 product dip time in liquid carbon dioxide is 1-1.5h；The condition of supercritical drying is：Drying temperature is
45-48 DEG C, drying pressure 8-10MPa, drying time 6-8h.
5. the preparation method of polysilazane-zirconium dioxide aerogel composite, it is characterised in that follow the steps below：
Step 1, polysilazane precursor is scattered in toluene, sequentially adds tetrabutyl zirconate and divinylbenzene, stir rapidly
Mix and uniformly obtain mixing weak solution, above-mentioned mixing weak solution is transferred in hydrothermal reaction kettle and sealed, it is dilute molten that mixing will be filled
The reactor of liquid is placed in 160-200 DEG C of drying box after reaction 1-6h, is cooled to 20-25 DEG C of room temperature, is obtained wet gel, by described in
Wet gel is put into the beaker for filling toluene, stands 24-36h；
Step 2, step 1 product is transferred in carbon dioxide supercritical extraction device, 0.5- is impregnated in liquid carbon dioxide
2.0h, after then carrying out supercritical drying, that is, obtain polysilazane-zirconium dioxide aerogel composite；
In step 1, polysilazane precursor be 4-10 parts by weight, the toluene of scattered polysilazane precursor be 4-10 weight
Part, tetrabutyl zirconate are 0.5-2.5 parts by weight, divinylbenzene is 4-8 parts by weight；Polysilazane is linear structure, main chain by
Si, N atom are alternate to be formed, and has Si -- H bond in structure, and has vinyl sidechain, and its molal weight is 800-1500g/mol；
In step 2, the condition of supercritical drying is：Drying temperature is 40-50 DEG C, drying pressure 5-10MPa, drying time 5-
9h。
6. the preparation method of polysilazane according to claim 1-zirconium dioxide aerogel composite, its feature exist
In, in step 1, polysilazane precursor is 5-8 parts by weight, the toluene of scattered polysilazane precursor be 5-8 parts by weight,
Tetrabutyl zirconate is 1-2 parts by weight, divinylbenzene is 5-6 parts by weight, and the molal weight of polysilazane is 1000-1200g/
mol。
7. the preparation method of polysilazane according to claim 1-zirconium dioxide aerogel composite, its feature exist
In in step 1, the reactor for filling mixing weak solution reacts 2-5h in 180-200 DEG C of drying box；Wet gel
It is put into beaker, wet gel is submerged with toluene, stands 25-30 hours.
8. the preparation method of polysilazane according to claim 1-zirconium dioxide aerogel composite, its feature exist
In in step 2, step 1 product dip time in liquid carbon dioxide is 1-1.5h；The condition of supercritical drying is：It is dry
Dry temperature is 45-48 DEG C, drying pressure 8-10MPa, drying time 6-8h.
9. polysilazane as claimed in claim 1-zirconium dioxide aerogel composite synthetic dyestuffs in the aqueous solution is removed
In application, such as methylene blue.
10. polysilazane as claimed in claim 1-zirconium dioxide aerogel composite should waterproof or heat-insulated field
With.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114753025A (en) * | 2022-05-10 | 2022-07-15 | 中国人民解放军国防科技大学 | High-strength high-toughness silica carbon fiber and preparation method and application thereof |
| CN114853470A (en) * | 2022-05-30 | 2022-08-05 | 天津城建大学 | Enhanced thermal insulation zirconium dioxide composite ceramic aerogel and preparation method thereof |
| CN115819093A (en) * | 2022-10-17 | 2023-03-21 | 杭州清瓷新材料科技有限公司 | Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114753025A (en) * | 2022-05-10 | 2022-07-15 | 中国人民解放军国防科技大学 | High-strength high-toughness silica carbon fiber and preparation method and application thereof |
| CN114853470A (en) * | 2022-05-30 | 2022-08-05 | 天津城建大学 | Enhanced thermal insulation zirconium dioxide composite ceramic aerogel and preparation method thereof |
| CN114853470B (en) * | 2022-05-30 | 2022-12-09 | 天津城建大学 | Enhanced thermal insulation zirconium dioxide composite ceramic aerogel and preparation method thereof |
| CN115819093A (en) * | 2022-10-17 | 2023-03-21 | 杭州清瓷新材料科技有限公司 | Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof |
| CN115819093B (en) * | 2022-10-17 | 2023-10-24 | 杭州清瓷新材料科技有限公司 | Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof |
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