CN106189066A - A kind of phenolic resin/silicon dioxide composite aerogel material and preparation method thereof - Google Patents
A kind of phenolic resin/silicon dioxide composite aerogel material and preparation method thereof Download PDFInfo
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- CN106189066A CN106189066A CN201610523335.0A CN201610523335A CN106189066A CN 106189066 A CN106189066 A CN 106189066A CN 201610523335 A CN201610523335 A CN 201610523335A CN 106189066 A CN106189066 A CN 106189066A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
- C08G8/22—Resorcinol
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- 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
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08L2201/00—Properties
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Abstract
The invention provides a kind of phenolic resin/silicon dioxide composite aerogel material and preparation method thereof, described phenolic resin/silicon dioxide composite aerogel material has silicon dioxide phase and the intermeshing Specific surface area of resin-phase；By including the material of organosilane precursor, phenolic compound, aldehyde compound and chitosan, sol-gal process and supercritical carbon dioxide is utilized to be dried prepared.In the aerogel composite that the present invention provides, organic facies and inorganic phase respectively continuous print nanoscale tangles network, has the mechanical property of organic aerogel and the heat-insulating, fire-preventing ability of aerosil concurrently.This material thick for 1cm in the present invention can be under 1300 DEG C of torch flame, and anti-flame impingement without producing coming off and separating of inorganic phase, can guarantee that the temperature of protected side is less than 300 DEG C more than 30min simultaneously.The present invention is simple to operate, reacts safe and reliable, can be by the insulating refractory performance of simple material proportion change regulation and control resulting materials.
Description
Technical field
The present invention relates to aerogel material technical field, particularly relate to a kind of phenolic resin/silicon dioxide composite aerogel
Material and preparation method thereof.
Background technology
Aerogel material is a kind of material with three-dimensional net structure and extremely-low density, the earliest by American science worker
Kistler prepared in 1931.The three dimensional structure unique due to aeroge and physical property, its as fire-proof heat-insulating material by extensively
General apply in building, Aero-Space and other high-tech areas.The aeroge with application prospect of report mainly wraps at present
Include two classes: 1, the inorganic gas that the inorganic nano unit with aerosil, graphite oxide aerogel etc. as representative is constructed
Gel rubber material；2, the organic aerogel material with polyurethane aeroge, phenolic resin aerogel, epoxy resin aeroge as representative
Material.But, the fire protecting performance that common are machine aeroge does not reaches the fire prevention level of inorganic aerogels；Common inorganic aerogels
The application of material is limited to again the mechanical property that it is extremely brittle, and these all propose new higher material to researchers and prepare
Requirement.
The inorganic phase of rigidity and the organic facies with flexibility being combined, this is that the performance improving the materials such as aeroge provides
A kind of method with development prospect.Such as, " JACS " (Journal of the American Chemical
Society, the 136th phase in 2014, page 16066) report and a kind of assembled altogether by inorganic matter presoma and block copolymer
To ordered mesopore structure, then in-situ polymerization Organic substance, obtain a kind of porous organic inorganic hybridization rich in Organic substance microfacies and be combined
Material；U.S.'s " polymer science magazine " (Journal of Polymer Science Part A:Polymer
Chemistry, the 41st phase in 2003, page 905) report a kind of by sol-gel method, prepare thermoplastic phenolic resin
Fat and the nano composite material of silicon dioxide.
But, all there is a major issue in said method, it is simply that cannot be avoided between material organic facies and inorganic phase
It is separated.When, in continuous print combustion process, along with the ablation of organic facies, seeing due to two alternate Jie or macroface separated
Journey, inorganic phase can come off rapidly, makes material can not continue to keep the performance of heat-insulating, fire-preventing.
Summary of the invention
In view of this, the application provides a kind of phenolic resin/silicon dioxide composite aerogel material and preparation method thereof, this
The aerogel material that invention provides has the heat-insulating, fire-preventing performance of excellence.
The present invention provides a kind of phenolic resin/silicon dioxide composite aerogel material, by including organosilane precursor, phenols
The material of compound, aldehyde compound and chitosan, utilizes sol-gal process and supercritical carbon dioxide to be dried prepared；
Described phenolic resin/silicon dioxide composite aerogel material has silicon dioxide phase and resin-phase is intermeshing receives
Rice network structure.
Preferably, the density of described phenolic resin/silicon dioxide composite aerogel material is 27～48mg/cm3。
Preferably, the porosity of described phenolic resin/silicon dioxide composite aerogel material is more than 97%.
Preferably, in described phenolic resin/silicon dioxide composite aerogel material, the mass content of silicon dioxide is 20%
～90%.
The present invention also provides for the preparation method of a kind of phenolic resin/silicon dioxide composite aerogel material, including following step
Rapid:
A) in presence of an acid, organosilane precursor and phenolic compound are disperseed in aqueous solution, makes organosilicon forerunner
Body hydrolyzes, and obtains mixed solution；
B) described mixed solution is mixed with chitosan, aldehyde compound and water, form colloidal sol, then carry out hydro-thermal anti-
Should, obtain phenolic resin/silicon dioxide composite aquogel；
C) described phenolic resin/silicon dioxide composite aquogel is carried out supercritical carbon dioxide to be dried, obtain phenolic aldehyde tree
Fat/silicon dioxide composite aerogel material.
Preferably, in described step a), one or more in formic acid, acetic acid and oxalic acid of described acid；
At least one in tetraethyl orthosilicate and methyl silicate of described organosilane precursor.
Preferably, in described step a), the volume of described acid, the volume of organosilane precursor, the material of phenolic compound
The ratio of amount and the volume of aqueous solution be (0.2～0.8) mL:(1～8) mL:(0.01～0.02) mol:30mL.
Preferably, in described step a), described hydrolysis is at room temperature carried out, and the time of described hydrolysis is 4h～24h.
Preferably, described step c) particularly as follows:
Described phenolic resin/silicon dioxide composite aquogel is carried out solvent displacement, then carries out supercritical carbon dioxide
It is dried, obtains phenolic resin/silicon dioxide composite aerogel material.
Preferably, also include:
D) described phenolic resin/silicon dioxide composite aerogel material is compressed, the phenolic resin after being compressed/
Silicon dioxide composite aerogel material.
Compared with prior art, phenolic resin/silicon dioxide composite aerogel material that the present invention provides has titanium dioxide
Silicon phase and the intermeshing Specific surface area of resin-phase, by include organosilane precursor, phenolic compound, aldehyde compound and
The material of chitosan, utilizes sol-gal process and supercritical carbon dioxide to be dried prepared.The composite aerogel material that the present invention provides
In material, organic facies and inorganic phase respectively continuous print nanoscale tangles network, has the mechanical property and two of organic aerogel concurrently
The heat-insulating, fire-preventing ability of silica aerogel.In the present invention, this thick for 1cm material can under the torch flame of 1300 DEG C,
Anti-flame impingement without producing coming off and separating of inorganic phase more than more than 30min, simultaneously can also ensure that and protected
The temperature of side is less than 300 DEG C, heat-insulating, fire-preventing excellent performance.
Further, the present invention is simple to operate, reacts safe and reliable, it is possible to regulate and control institute by the change of simple material proportion
Obtain the insulating refractory performance of material, be suitable to large-scale industrial and promote.
Accompanying drawing explanation
Fig. 1 is the photo in kind of the phenolic resin/silicon dioxide dual network composite aquogel of the embodiment of the present invention 1 preparation；
Fig. 2 is the photo in kind of the phenolic resin/silicon dioxide dual network aeroge of the embodiment of the present invention 1 preparation；
Fig. 3 is the stereoscan photograph of the phenolic resin/silicon dioxide dual network aeroge of the embodiment of the present invention 1 preparation；
Fig. 4 is the transmission electron microscope photo of the phenolic resin/silicon dioxide dual network aeroge of the embodiment of the present invention 1 preparation；
Fig. 5 is the high-resolution transmission electricity of the phenolic resin carbon/silicon dioxide dual network aeroge of the embodiment of the present invention 1 preparation
Mirror photo；
Fig. 6 is that the resorcinol formaldehyde resin/silicon dioxide dual network composite aquogel of the embodiment of the present invention 2 preparation is gentle
The photo figure in kind of gel；
Fig. 7 is the stereoscan photograph of the phenolic resin/silicon dioxide dual network aeroge of the embodiment of the present invention 3 preparation；
Fig. 8 is that the transmission electron microscope of the phenolic resin carbon/silicon dioxide dual network aeroge of the embodiment of the present invention 3 preparation shines
Sheet；
Fig. 9 is the stereoscan photograph of the phenolic resin/silicon dioxide dual network aeroge of the embodiment of the present invention 4 preparation；
Figure 10 is that the transmission electron microscope of the phenolic resin carbon/silicon dioxide dual network aeroge of the embodiment of the present invention 4 preparation shines
Sheet；
Figure 11 is the stereoscan photograph of the phenolic resin/silicon dioxide dual network aeroge of the embodiment of the present invention 5 preparation；
Figure 12 is that the transmission electron microscope of the phenolic resin carbon/silicon dioxide dual network aeroge of the embodiment of the present invention 5 preparation shines
Sheet；
Figure 13 is the close of the phenolic resin/silicon dioxide dual network aeroge of different silicone contents prepared by the embodiment of the present invention
Degree delta data figure；
Figure 14 is the heat of the phenolic resin/silicon dioxide dual network aeroge of different silicone contents prepared by the embodiment of the present invention
Weight analysis figure；
Figure 15 is the power of the phenolic resin/silicon dioxide dual network aeroge of different silicone contents prepared by the embodiment of the present invention
Learn compression stress strain figure；
Figure 16 be embodiment 1 preparation unpressed aerogel material and embodiment 7 compression after phenolic resin/titanium dioxide
The contrast photo in kind of silicon dual network aeroge；
Figure 17 is the schematic diagram of embodiment of the present invention fire resistance test device；
Figure 18 is the fire resistance test photo of embodiment of the present invention aerogel material；
Figure 19 is the temperature versus time curve of embodiment 1 unpressed aerogel material back-fire side；
Figure 20 is the temperature versus time curve of the aerogel material back-fire side after embodiment 7 compression；
Figure 21 is that the material object after the aeroge ablation after the unpressed aerogel material of embodiment 1 and embodiment 7 compression is right
According to sheet；
Figure 22 is the ablation situation of phenolic resin aerogel prepared by comparative example.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment
It is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
The invention provides a kind of phenolic resin/silicon dioxide composite aerogel material, by including organosilane precursor, phenol
The material of compounds, aldehyde compound and chitosan, utilizes sol-gal process and supercritical carbon dioxide to be dried prepared；Described
Phenolic resin/silicon dioxide composite aerogel material has silicon dioxide phase and the intermeshing Specific surface area of resin-phase.
Phenolic resin/silicon dioxide composite aerogel material that the present invention provides has extremely-low density concurrently and the heat insulation of excellence prevents
The performance of ablation fiery, resistance to, is beneficial to application.
Phenolic resin/silicon dioxide composite aerogel material that the present invention provides has silicon dioxide phase and resin-phase is mutual
The Specific surface area tangled, i.e. organic facies and inorganic phase respectively continuous print nanoscale tangles network, this microcosmic nanometer
Dual network structure is unique, novel.This material is phenolic resin/silicon dioxide dual network aeroge, network of silica and resin
Network mutually tangles, and has the mechanical property of organic aerogel and the heat-insulating, fire-preventing ability of aerosil concurrently.Different ratio
Dual network aeroge in, dioxide-containing silica is different, and organosilane precursor addition is the most, in gained dual network aeroge two
The content of silica network is the highest.In described phenolic resin/silicon dioxide composite aerogel material, the mass content of silicon dioxide
It is preferably 20～90%, more preferably 22～85%.The embodiment of the present invention, can be by obtained material by different proportionings
Middle dioxide-containing silica basic controlling is 22.9～82.5%.
In some embodiments of the invention, the network fibres thickness of described dual network aeroge is 10nm～20nm.?
In some embodiments of the present invention, the density of described phenolic resin/silicon dioxide composite aerogel material is 27～48mg/cm3,
It is preferably 30～40mg/cm3.The porosity of described phenolic resin/silicon dioxide composite aerogel material preferably more than 97%,
Such as 97.1%, 97.8%, 98% etc..In some embodiments of the invention, described phenolic resin/silicon dioxide composite aerogel
The specific surface area of material can be 155～450m2/g。
In the present invention, described phenolic resin/silicon dioxide composite aerogel material is by including organosilane precursor, phenols
The material of compound, aldehyde compound and chitosan, utilizes sol-gal process and supercritical carbon dioxide to be dried prepared.Wherein,
Described organosilane precursor preferably is selected from least one in tetraethyl orthosilicate and methyl silicate.Described phenolic compound is preferred
A kind of or any proportioning in phenol, resorcinol and phloroglucinol several, more preferably phenol or resorcinol.Described
Aldehyde compound preferably is selected from one or more in formaldehyde, paraformaldehyde and acetaldehyde, more preferably formaldehyde.Enforcement in the present invention
In example, described chitosan can be the commercially available prod of Shanghai traditional Chinese medicines group.
Phenolic resin/silicon dioxide dual network aeroge that the present invention provides, owing to introducing organic facies and inorganic phase two
Plant intermeshing Specific surface area, effectively improve the non-plastic fracture in compression process of the traditional silicon dioxide aeroge
Problem, meanwhile, also greatly strengthen the fire resistance property of tradition organic aerogel.In dual network aeroge of the present invention, organic facies and
The phase separation occurred between inorganic phase is nanoscale, has higher interaction so that this material is at high temp fire
In the ablation process of flame, inorganic phase will be caused to peel off because of the loss of the sintering of organic facies, improve the service life of material, greatly
Extend greatly the range of application of material.This novel aeroge can also pass through precommpression, to improve the mechanical property of material,
Reduce material taking volume and using volume in transportation, the energy of resistance to ablation of material can also be further enhanced simultaneously
Power.
Present invention also offers the preparation method of a kind of phenolic resin/silicon dioxide composite aerogel material, including following
Step:
A) in presence of an acid, organosilane precursor and phenolic compound are disperseed in aqueous solution, makes organosilicon forerunner
Body hydrolyzes, and obtains mixed solution；
B) described mixed solution is mixed with chitosan, aldehyde compound and water, form colloidal sol, then carry out hydro-thermal anti-
Should, obtain phenolic resin/silicon dioxide composite aquogel；
C) described phenolic resin/silicon dioxide composite aquogel is carried out supercritical carbon dioxide to be dried, obtain phenolic aldehyde tree
Fat/silicon dioxide composite aerogel material.
The preparation method that the present invention provides can prepare above-mentioned phenolic resin/bis-with the excellent thermal insulation resistance to ablation ability of fire prevention
Silicon oxide dual network aerogel material, the method is simple and reliable, and raw material is easy to get, cheap, the most less, is suitable to extensive work
Industry popularization and application.
The embodiment of the present invention can add aqueous solution, phenolic compound, organosilane precursor and acid in the reactor, carries out
Hydrolysis, after hydrolysis, obtains mixed solution, is designated as solution A.Described reactor can be beaker commonly used in the art, after charging
Sealing stirring, makes organosilane precursor hydrolyze；Charging sequence is also not particularly limited by the present invention.
In the present invention, at least during described organosilane precursor preferably is selected from tetraethyl orthosilicate and methyl silicate
Kind.A kind of or any proportioning that described phenolic compound preferably is selected from phenol, resorcinol and phloroglucinol several, more preferably
For phenol or resorcinol.Described acid preferably is selected from one or more in formic acid, acetic acid and oxalic acid, more preferably acetic acid (ice vinegar
Acid).
Above-mentioned acid, organosilane precursor and phenolic compound can be disperseed in aqueous solution by the embodiment of the present invention, stirring,
There is hydrolysis, to promote to produce between inorganic matter monomer and Orqanics Monomer hydrogen bond action, promote prepolymerization.Described aqueous
Solution is preferably water or the mixed solution of the mixed solution of water/dehydrated alcohol, more preferably water and dehydrated alcohol.The present invention's
In preferred embodiment, in described water/dehydrated alcohol mixed solution, the volume parts of dehydrated alcohol can be 1/3～3/4, preferably 1/
2～3/4.In some embodiments of the invention, the volume of described acid, the volume of organosilane precursor, the thing of phenolic compound
The amount of matter is preferably (0.2～0.8) mL:(1～8 with the ratio of the volume of aqueous solution) mL:(0.01～0.02) mol:30mL, more
It is preferably (0.6～0.8) mL:(4～6) mL:(0.01～0.02) mol:30mL.
In the present invention, the time of the hydrolysis of described organosilane precursor is preferably 4h～24h, more preferably 8h～24h,
Most preferably 16h～24h.The hydrolytic process of described organosilane precursor can at room temperature be carried out, the most special restriction, also
Need not special temperature adjusting；In general, the scope of room temperature can be regarded as 15～30 DEG C.
After obtaining mixed solution (solution A), it is mixed by the embodiment of the present invention with chitosan, aldehyde compound and water, all
After even stirring, form colloidal sol.Solution A and chitosan solution are the most first mixed by the present invention, and are added thereto to aldehyde compound,
Continuing vigorous stirring certain time, form colloidal sol.
Wherein, described chitosan solution can be dispersed in water by chitosan, stirs, and to obtain final product, and can be designated as solution B.?
In embodiments of the invention, described chitosan can be the commercially available prod of Shanghai traditional Chinese medicines group.Chitosan environmental protection, price is low
Honest and clean, the present invention uses chitosan colloidal sol network as template, to support Orqanics Monomer and inorganic matter monomer, promotes plastic.Institute
Stating in solution B, the quality of chitosan is preferably (0.1～0.5) g:15mL with the ratio of the volume of water, more preferably (03～0.5)
G:15mL..
Solution A is preferably quickly poured into solution B by the present invention, stirring, adds aldehyde compound solution, and continuing vigorous stirs
10min, forms the colloidal sol of mixing.Described aldehyde compound preferably is selected from one or more in formaldehyde, paraformaldehyde and acetaldehyde, more
It is preferably formaldehyde.In some embodiments of the invention, the formalin of 37wt% can be used.In an embodiment of the present invention,
The consumption of described aldehyde compound is preferably 0.02mol～0.04mol.
After obtaining colloidal sol, the embodiment of the present invention is loaded into hydrothermal reaction kettle, is placed in baking oven and carries out hydro-thermal reaction, obtains
Phenolic resin/silicon dioxide composite aquogel.Wherein, described hydrothermal reaction kettle preferably has teflon-lined reaction
Still.The present invention uses hydrothermal synthesis method, the directly combined polymerization on chitosan gel rubber framework by Organic substance and inorganic matter, is answered
Heshui gel.The temperature of described hydro-thermal reaction is preferably 100～200 DEG C, more preferably 100～160 DEG C；The time of hydro-thermal reaction
It is preferably 8h～24h, more preferably 10h～16h.
After obtaining composite aquogel, the embodiment of the present invention is passed through supercritical carbon dioxide (CO2) be dried method, put
Change dry, effectively remove the solvent in hydrogel, retain gel network structure, obtain organic inorganic hybridization dual network aeroge,
I.e. phenolic resin/silicon dioxide composite aerogel material.The essence of supercritical carbon dioxide dry technology is by hydrogel
Solvent is replaced by supercritical carbon dioxide, reaches the purpose of desiccant gel；In temperature higher than critical temperature, pressure is higher than
Under conditions of critical pressure, supercritical carbon dioxide can be obtained, material is dried.
Described phenolic resin/silicon dioxide composite aquogel is preferably carried out solvent displacement by the present invention, then carries out super facing
Boundary's carbon dioxide is dried, and obtains phenolic resin/silicon dioxide composite aerogel material.Concrete, the embodiment of the present invention is by described
Phenolic resin/carbon dioxide dual network composite aquogel soaks and carries out repeatedly replacement operator in organic solvent, multiple to dual network
Solvent in Heshui gel is replaced, feeding, carries out supercritical drying, obtains phenolic resin/carbon dioxide dual network airsetting
Glue.Wherein, described organic solvent is preferably acetone or dehydrated alcohol.Displacement number of times is different because of material and experiment condition with the time,
The organic solvent that can displace is faded to colourless for completing standard by rufous or brown color, and the present invention is to supercritical carbon dioxide
Dry technology is not particularly limited, and the temperature used can be 55 DEG C, and pressure is 100atm.
The present invention the most also includes: is compressed by described phenolic resin/silicon dioxide composite aerogel material, is pressed
Phenolic resin after contracting/silicon dioxide composite aerogel material.
The present invention can reduce aeroge internal voids size further by the method for compression, and this method both can reach
To the purpose of enhancing aeroge frame strength, the ability of the resistance to ablation of material heat-insulating, fire-preventing can be further enhanced again, it is also possible to subtract
Few material taking volume and using volume in transportation.The compression speed of described compression is preferably 1～5mm/min, more
It is preferably 2～5mm/min.
After obtaining phenolic resin/silicon dioxide composite aerogel material, the present invention carries out performance test to it.By surveying
Examination, the density of phenolic resin prepared by the present invention/silicon dioxide dual network aeroge is only 27～48mg/cm3, have less than sky
The thermal conductivity of gas and excellent fire resistance.When this thick for former 2cm dual network aeroge is compressed to 1cm thickness, material has still preserved
Good, and can be under the torch flame of 1300 DEG C, shock resistance is more than more than 30min, and ensure that the temperature of protected side
Less than 300 DEG C, the basic standard of aerospace material can be reached.
The present invention is simple to operate, reacts safe and reliable, can prepare with magnanimity, it is possible to adjusted by the change of simple material proportion
The insulating refractory performance of control resulting materials；Material prepared by the present invention has the heat-insulating, fire-preventing performance of excellence, can pass through simultaneously
Precommpression reduces transport and uses volume, improves resistance to ablation ability, before having broader practice than traditional aerogel material
Scape.
In order to be further appreciated by the application, the phenolic resin/silicon dioxide provided the application below in conjunction with embodiment is multiple
Close aerogel material and preparation method thereof to be specifically described.
In following example, each raw material is the most commercially available；The model of supercritical carbon dioxide drying machine used is Spe-
Ed SFE-helix, baking temperature is 55 DEG C, and pressure is 100atm.
Embodiment 1
The present embodiment phenolic resin/silicon dioxide dual network aeroge is carried out as follows:
A, in the beaker that volume is 50mL, add 15mL water and 15mL dehydrated alcohol, and be added thereto to 1.882g benzene
Phenol, 6mL tetraethyl orthosilicate and 0.6mL glacial acetic acid, sealing, 24h is stirred at room temperature, is hydrolyzed, gained mixed solution is designated as molten
Liquid A；
B, in another beaker, 0.45g chitosan (Shanghai traditional Chinese medicines group, No. CAS: 9012-76-4) is dispersed in
In 15mL water, gained chitosan solution is designated as solution B；
Solution A being poured in solution B rapidly, and be added thereto to 3mL formalin (37wt% formaldehyde), continuing vigorous stirs
Mix 10min, form colloidal sol；
Described colloidal sol being loaded 50mL teflon-lined hydrothermal reaction kettle, is placed in the baking oven of 160 DEG C, hydro-thermal is anti-
Answer 10h, obtain phenolic resin/silicon dioxide dual network composite aquogel (hybrid gel) of yellow.
C, described hybrid gel submergence is soaked three days in acetone, the acetone more renewed every day, until acetone is colourless, so
The rear hybrid gel taken out after replacing, carries out supercritical carbon dioxide and is dried, obtain phenolic resin/silicon dioxide dual network airsetting
Glue.
The photo in kind of the phenolic resin obtained in the present embodiment/silicon dioxide dual network composite aquogel and aeroge is such as
Shown in Fig. 1, Fig. 2, Fig. 1 is that the material object of the phenolic resin/silicon dioxide dual network composite aquogel of the embodiment of the present invention 1 preparation shines
Sheet, Fig. 2 is the photo in kind of the phenolic resin/silicon dioxide dual network aeroge of the embodiment of the present invention 1 preparation.
Phenolic resin/silicon dioxide dual network the aeroge of embodiment 1 preparation is denoted as PS-6, phenolic resin/silicon dioxide
The stereoscan photograph of dual network aeroge is as it is shown on figure 3, Fig. 3 is phenolic resin/silicon dioxide prepared by the embodiment of the present invention 1
The stereoscan photograph of dual network aeroge.As shown in Figure 4, Fig. 4 is the phenol of the embodiment of the present invention 1 preparation to its transmission electron microscope photo
The transmission electron microscope photo of urea formaldehyde/silicon dioxide dual network aeroge.
For the ease of observing test, this dual network aeroge is carried out high temperature cabonization by the present embodiment, and Carbonization Conditions is: nitrogen
Under atmosphere protection, 5 DEG C/min is warming up to 800 DEG C, and carbonization 2h under 800 DEG C of environment.Dual network aeroge after carbonization is entered
Row high-resolution-ration transmission electric-lens is observed, as it is shown in figure 5, phenolic resin carbon/silicon dioxide that Fig. 5 is the embodiment of the present invention 1 preparation is double
The high-resolution-ration transmission electric-lens photo of network aeroge.As seen from Figure 5, the dual network aeroge that this embodiment prepares
Network fibres thickness is 10nm～20nm, and network of silica and resin carbon network mutually tangle.
Embodiment 2
Utilize the preparation method identical with embodiment 1:
A, in the beaker that volume is 50mL, add 10mL water and 20mL dehydrated alcohol, and be added thereto between 2.202g
Benzodiazepines, 6mL methyl silicate and 0.6mL glacial acetic acid, sealing, 24h is stirred at room temperature, is hydrolyzed, gained mixed solution is designated as
Solution A；
B, in another beaker, 0.45g chitosan (Shanghai traditional Chinese medicines group, No. CAS: 9012-76-4) is dispersed in
In 15mL water, gained chitosan solution is designated as solution B；
Solution A being poured in solution B rapidly, and be added thereto to 3mL formalin (37wt% formaldehyde), continuing vigorous stirs
Mix 10min, form colloidal sol；
Described colloidal sol being loaded 50mL teflon-lined hydrothermal reaction kettle, is placed in the baking oven of 100 DEG C, hydro-thermal is anti-
Answer 10h, obtain resorcinol formaldehyde resin/silicon dioxide dual network composite aquogel (hybrid gel).
C, described hybrid gel submergence is soaked three days in acetone, the acetone more renewed every day, until acetone is colourless, so
The rear hybrid gel taken out after replacing, carries out supercritical carbon dioxide and is dried, and obtains resorcinol formaldehyde resin/silicon dioxide double
Network aeroge.
The resorcinol formaldehyde resin obtained in the present embodiment/silicon dioxide dual network composite aquogel and the reality of aeroge
As shown in Figure 6, Fig. 6 is the resorcinol formaldehyde resin/silicon dioxide dual network Compound Water of the embodiment of the present invention 2 preparation to thing photo
Gel and the photo figure in kind of aeroge.
Embodiment 3～5
Utilize the preparation method identical with embodiment 1, step a is added the positive silicic acid tetrem of 2mL, 4mL and 8mL respectively
Ester；The phenolic resin obtained/silicon dioxide dual network aeroge is denoted as PS-2, PS-4 and PS-8 respectively.
The stereoscan photograph of gained aerogel material and transmission electron microscope photo are respectively as shown in Fig. 7 to Figure 12, and Fig. 7 is this
The stereoscan photograph of the phenolic resin/silicon dioxide dual network aeroge of inventive embodiments 3 preparation, Fig. 8 is that the present invention implements
The transmission electron microscope photo of the phenolic resin carbon/silicon dioxide dual network aeroge of example 3 preparation, Fig. 9 is prepared by the embodiment of the present invention 4
The stereoscan photograph of phenolic resin/silicon dioxide dual network aeroge, Figure 10 is the phenolic aldehyde tree of the embodiment of the present invention 4 preparation
The transmission electron microscope photo of fat carbon/silicon dioxide dual network aeroge, Figure 11 is phenolic resin/bis-of the embodiment of the present invention 5 preparation
The stereoscan photograph of silicon oxide dual network aeroge, Figure 12 is the phenolic resin carbon/silicon dioxide of the embodiment of the present invention 5 preparation
The transmission electron microscope photo of dual network aeroge.
Embodiment 6
1, by nitrogen adsorption analytic process i.e. BET specific surface area method of testing, the specific surface area of following different materials is tested
(SBET), pore volume (Vpore), average void width (APW) and porosity.Result sees table 1, and table 1 is embodiment 1 and 3～5 system
The porosity etc. of standby phenolic resin carbon/silicon dioxide dual network aeroge.
The porosity etc. of the phenolic resin carbon/silicon dioxide dual network aeroge of table 1 embodiment 1 and 3～5 preparation
| Sample number into spectrum | PS-2 | PS-4 | PS-6 | PS-8 |
| SBET(m2/g) | 157.6 | 408.9 | 400 | 399 |
| Vpore(cm3/g) | 0.903 | 0.74 | 0.72 | 0.67 |
| APW(nm) | 22.9 | 9.2 | 10.1 | 9.02 |
| Porosity (%) | 98 | 97.9 | 97.8 | 97.1 |
From table 1 data above, the sample of specific surface area maximum is PS-4, reaches 408.9m2/g；Porosity maximum
Sample is PS-2, is 98%；The porosity of all samples is all more than 97% simultaneously, and the aeroge material that the present invention synthesizes is described
Material has the highest porosity.
2, by testing the weight and volume of aeroge, the phenolic resin carbon/titanium dioxide of embodiment 1 and 3～5 preparation is calculated
The density of silicon dual network aeroge, each group of data test 5, calculate meansigma methods.As shown in figure 13, Figure 13 is the present invention to result
The density variance data figure of the phenolic resin of different silicone contents prepared by embodiment/silicon dioxide dual network aeroge.By airsetting
Glue density map understands, along with the increase of organosilane precursor content, obtained phenolic resin/silicon dioxide dual network aeroge
Density also increase, substantially present linear change.The density of phenolic resin prepared by the present invention/silicon dioxide dual network aeroge
It is only 27～48mg/cm3, there is extremely-low density.
Phenolic resin carbon/silicon dioxide dual network the aeroge using thermogravimetric analyzer to prepare embodiment 1 and 3～5 enters
Row thermogravimetric analysis, test condition is: ignition temperature is 800 DEG C, and heating rate is 10 DEG C/min, and atmosphere is air.Result such as figure
Shown in 14, Figure 14 is the heat of the phenolic resin/silicon dioxide dual network aeroge of different silicone contents prepared by the embodiment of the present invention
Weight analysis figure.From thermogravimetric analysis figure, in the dual network aeroge obtained by different ratio, dioxide-containing silica is different
's.Organosilane precursor addition is the most, and in gained dual network aeroge, the content of network of silica is the highest；By different
Proportioning, in obtained material, the content of silicon dioxide can be with basic controlling between 22.9%～82.5%.
By mechanical test instrument (model Instron 5565A), phenolic resin carbon/bis-to embodiment 1 and 3～5 preparation
Silicon oxide dual network aeroge is compressed stress-strain test, specifically includes: be positioned on test platform by sample, and compression passes
Sensor size is 500N, and compression speed is 2mm/min.As shown in figure 15, Figure 15 is difference prepared by the embodiment of the present invention to result
The mechanics compression stress strain figure of the phenolic resin of silicone content/silicon dioxide dual network aeroge.By the compression of aerogel material
Stress-strain diagram understands, and the mechanical property of aerogel material prepared by the embodiment of the present invention presents non-response moulding shape
Become.Meanwhile, the addition of organosilane precursor is the most, obtained phenolic resin/silicon dioxide dual network aerogel material
Modulus of compressibility is the highest, and material stiffness is the strongest.
According to above test result, owing to adding the difference of the amount of organosilane precursor, obtained dual network aeroge
Density, mechanical property the most different.
Embodiment 7
Utilizing the preparation method identical with embodiment 1, aerogel material is carried out precommpression, compression speed is 2mm/min,
Compression strain is 50%, the phenolic resin/silicon dioxide dual network aerogel material after preparation compression.Embodiment 1 is unpressed
The in kind of phenolic resin/silicon dioxide dual network aeroge after aeroge and embodiment 7 compression contrasts photo as shown in figure 16,
Figure 16 be embodiment 1 preparation unpressed aerogel material and embodiment 7 compression after phenolic resin/silicon dioxide dual network
The contrast photo in kind of aeroge.
Embodiment 8
For the use environment of more preferable simulating reality heat-insulating fire-proofing material, further illustrate phenolic aldehyde tree prepared by the present invention
The excellent properties of fat/silicon dioxide dual network aeroge, the present embodiment use propane/butane blowtorch to embodiment 1 uncompressed and
Aerogel material after embodiment 7 compression carries out ablation, and utilizes aeroge in infrared thermography real time record ablation process
The variations in temperature of material back-fire side.
As shown in figure 17, as shown in figure 18, Figure 17 is this to test photo to the schematic diagram of whole fire resistance test device
The schematic diagram of bright embodiment fire resistance test device, Figure 18 is that the fire resistance test of embodiment of the present invention aerogel material is shone
Sheet.As shown in figure 19, Figure 19 is the unpressed airsetting of embodiment 1 to the situation of embodiment 1 unpressed aerogel material back-fire side
The temperature versus time curve of glue material back-fire side；The situation such as figure of the aerogel material back-fire side after embodiment 7 compression
Shown in 20, Figure 20 is the temperature versus time curve of the aerogel material back-fire side after embodiment 7 compression.Ablation 30min
After, the contrast photo in kind of the phenolic resin/silicon dioxide dual network aeroge after uncompressed and compression as shown in figure 21, Figure 21
Contrast photo in kind after aeroge ablation after compressing for the unpressed aerogel material of embodiment 1 and embodiment 7.
It can be seen that the unpressed dual network aeroge of 2cm thickness is 1300 DEG C of torch flame from Figure 19 and Figure 20
Under continuous heating, dorsal part temperature was slowly increased to about 300 DEG C by room temperature in 20min, and moves closer to constant temperature, burning 20 minutes
After, material dorsal part mean temperature reaches 310 DEG C；After dual network aeroge compression 50% thick for 2cm, at 30 minutes 1300 DEG C of blowtorch
In the ablation process of flame, the mean temperature of dorsal part only has 260 DEG C, and back surface is not also carbonized simultaneously.It should be noted that
As shown in figure 21, compressed after dual network aeroge not only ablation resistance promoted further, and due to compression make
Become the densification of network so that the material silicon dioxide in anti-flame impingement side does not fall off, and this also substantially increases
The service life of this phenolic resin/silicon dioxide dual network aerogel material and heat-insulating, fire-preventing resistance to ablation ability.
Comparative example
In the beaker that volume is 100mL, 0.45g chitosan (Shanghai traditional Chinese medicines group, No. CAS: 9012-76-4) is disperseed
In 30mL water, add the acetic acid of 0.6mL, stirring, it is thus achieved that water white chitosan colloidal sol；
9.411g liquid phenol is joined in above-mentioned chitosan colloidal sol, the most quickly stirring, mix homogeneously, form white
Emulsion, then it is rapidly added 3mL formalin (37wt% formaldehyde), keep quick continual stirring, obtain mixed sols；
Described mixed sols is loaded 50mL water heating kettle, is placed in the baking oven of 160 DEG C, hydro-thermal reaction 10h, obtains phenolic aldehyde tree
Fat organogel, can be described as organogel；
Described organogel submergence is soaked three days in acetone, the acetone more renewed every day, until acetone is colourless, then
Take out the organogel after displacement, carry out supercritical CO2It is dried, obtains phenolic resin aerogel.
The phenolic resin aerogel obtained is positioned over ablation on alcohol burner, and alcohol burner temperature is 500 DEG C～600 DEG C.Material
As shown in figure 22, Figure 22 is the ablation situation of phenolic resin aerogel prepared by comparative example, as seen from Figure 22, phenol to material ablation situation
Urea formaldehyde aeroge is in two minutes, complete by alcohol burner flame ablation.
From above-described embodiment and comparative example, phenolic resin prepared by the present invention/silicon dioxide dual network aeroge material
Material has low-density and excellent heat-insulating, fire-preventing ablation resistance simultaneously, it is possible under blowtorch, long-time ablation is without being broken
Bad, and the ablation resistance of material can be improved further by the method for compression on the premise of keeping material structure complete
Energy.The present invention can also regulate and control the density of gained aerogel material, power by regulation and control organic facies and the relative scale of inorganic phase
Learn performance and heat-insulating, fire-preventing performance etc..The present invention is simple to operate, reacts safe and reliable.
The above is only the preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel, on the premise of without departing from the technology of the present invention principle, are that by the multiple amendment to these embodiments, and these
Amendment also should be regarded as the scope that the present invention should protect.
Claims (10)
1. phenolic resin/silicon dioxide composite aerogel material, by including organosilane precursor, phenolic compound, aldehydes
Compound and the material of chitosan, utilize sol-gal process and supercritical carbon dioxide to be dried prepared；
Described phenolic resin/silicon dioxide composite aerogel material has silicon dioxide phase and the intermeshing nano net of resin-phase
Network structure.
Aerogel material the most according to claim 1, it is characterised in that described phenolic resin/silicon dioxide is combined airsetting
The density of glue material is 27～48mg/cm3。
Aerogel material the most according to claim 1, it is characterised in that described phenolic resin/silicon dioxide is combined airsetting
The porosity of glue material is more than 97%.
Aerogel material the most according to claim 1, it is characterised in that described phenolic resin/silicon dioxide is combined airsetting
In glue material, the mass content of silicon dioxide is 20%～90%.
5. a preparation method for phenolic resin/silicon dioxide composite aerogel material, comprises the following steps:
A) in presence of an acid, organosilane precursor and phenolic compound are disperseed in aqueous solution, makes organosilane precursor send out
Unboiled water solution, obtains mixed solution；
B) described mixed solution is mixed with chitosan, aldehyde compound and water, form colloidal sol, then carry out hydro-thermal reaction,
To phenolic resin/silicon dioxide composite aquogel；
C) described phenolic resin/silicon dioxide composite aquogel is carried out supercritical carbon dioxide to be dried, obtain phenolic resin/bis-
Silicon oxide aerogel composite.
Preparation method the most according to claim 5, it is characterised in that in described step a), described acid is selected from formic acid, acetic acid
With one or more in oxalic acid；
At least one in tetraethyl orthosilicate and methyl silicate of described organosilane precursor.
Preparation method the most according to claim 6, it is characterised in that in described step a), the volume of described acid, organosilicon
The volume of presoma, the amount of material and the ratio of the volume of aqueous solution of phenolic compound are (0.2～0.8) mL:(1～8) mL:
(0.01～0.02) mol:30mL.
Preparation method the most according to claim 5, it is characterised in that in described step a), described hydrolysis is at room temperature entered
OK, the time of described hydrolysis is 4h～24h.
Preparation method the most according to claim 5, it is characterised in that described step c) particularly as follows:
Described phenolic resin/silicon dioxide composite aquogel is carried out solvent displacement, then carries out supercritical carbon dioxide and be dried,
Obtain phenolic resin/silicon dioxide composite aerogel material.
10. according to the preparation method described in any one of claim 5～9, it is characterised in that also include:
D) described phenolic resin/silicon dioxide composite aerogel material is compressed, the phenolic resin/dioxy after being compressed
SiClx aerogel composite.
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| CN106189066B (en) | 2020-08-25 |
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