CN108395668A - A kind of hybrid phenol-formaldehyde resin and the preparation method and application thereof that silsesquioxane is modified - Google Patents
A kind of hybrid phenol-formaldehyde resin and the preparation method and application thereof that silsesquioxane is modified Download PDFInfo
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- CN108395668A CN108395668A CN201810139145.8A CN201810139145A CN108395668A CN 108395668 A CN108395668 A CN 108395668A CN 201810139145 A CN201810139145 A CN 201810139145A CN 108395668 A CN108395668 A CN 108395668A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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Abstract
The present invention relates to the hybrid phenol-formaldehyde resins and the preparation method and application thereof that a kind of silsesquioxane is modified, and belong to high performance resin based composites field.The hybrid phenol-formaldehyde resin that silsesquioxane provided in an embodiment of the present invention is modified, it reacts with phenolic resin by using POSS molecules shown in formula (1), it is the hybrid phenol-formaldehyde resin cured matter for being chemically crosslinked point to be formed with POSS molecules, obtain hybrid phenol-formaldehyde resin, nano-particle enhancing is played the role of in the addition of POSS hybrid molecules simultaneously, the maximum decomposition temperature of resin starting is increased to 580 DEG C or so by 450 DEG C of pure resin, it is residual it is heavy be increased to 65% or so by 58%, significantly improve the ablation resistance of material；The hybrid phenol-formaldehyde resin that POSS provided by the invention is modified has potential application prospect in the advanced thermally protective materials field of aerospace craft resin base.
Description
Technical field
The present invention relates to a kind of hybrid phenol-formaldehyde resin of half cage type polyhedral silsesquioxane (POSS) molecular modification and its
Preparation method belongs to high performance resin based composites field.
Background technology
With the continuous change of aerospace craft flight thermal environment, the materials demand of thermal protection system is also constantly become
Change.The appearance of near space vehicle so that ablative-type protective coating thermally protective materials will also face while in face of high temperature ablation environment
The test of aerobic environment.It, being capable of shape after ablation carbonization using phenolic resin as the resin base ablation thermal protection composite material of main base
At the carbon-coating structure of stable strong, washing away for hot-fluid is resisted, while increasing hyperthermia radiation effect.However under aerobic environment, burn
The porous silicon carbide layer formed is lost easily by O2Molecule corrodes, and then destroys carbon-coating structure, weakens the effect of hyperthermia radiation solar heat protection, very
It can extremely cause aerodynamic configuration that great change occurs, flight is caused to defeat.Therefore, space flight, military industry field are faced to ablative thermal protection composite wood
The increasingly harsh demand of material, to the inoxidizability of phenolic resin as matrix resin, ablation resistance, more stringent requirements are proposed.
The ablation of organosilicon compound phenol-formaldehyde resin modified and antioxygenic property have been reported that more in the literature.POSS conducts
The oligomer in organo-silicon compound with unique texture also has corresponding report in phenolic resin as matrix resin modification.In Yue
Wu et al. document (Polymer Bulletin, 2013,70:Octaphenyl POSS molecular modification heat is reported in 3261-3277)
The method of plastic phenolic resin, entire reaction system is using tetrahydrofuran as solvent medium, and obtained phenol-formaldehyde resin modified, this changes
Property phenolic resin initial decomposition temperature be increased to 385 DEG C by 312 DEG C of pure resin, but carbon yield is reduced to 58% left side by 65%
The right side, ablation resistance are remarkably decreased, and ablation efficiency reduces.
Invention content
The object of the present invention is to provide the hybrid phenol-formaldehyde resins and preparation method thereof that a kind of silsesquioxane is modified, and overcoming has
Oxidizable etc. the deficiency of machine silicon class compound modified phenolic resin matrix ablation resistance, ablation carburization zone.
For achieving the above object, the present invention provides the following technical solutions：
A kind of hybrid phenol-formaldehyde resin that silsesquioxane is modified, is made by silsesquioxane and phenolic resin cross-linking reaction,
The silsesquioxane has following molecular structure：
Wherein, R is isobutyl group, phenyl or iso-octyl, R1For H or
In an alternative embodiment, the mass ratio of the silsesquioxane and phenolic resin is 1:2~99.
A kind of preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane is modified, includes the following steps：
Step 1：Silsesquioxane is dissolved in alcohols solvent, silsesquioxane solution is obtained；
Step 2：The silsesquioxane solution is mixed with phenol resin solution, is stirred evenly, hybrid resin liquid is obtained；
Step 3, by the hybrid resin liquid at 50~70 DEG C vacuum pump drainage solvent, then elevated cure, obtains sesquialter
Silicone-modified hybrid phenol-formaldehyde resin.
In an alternative embodiment, the alcohols solvent described in step 1 is methanol, ethyl alcohol or isopropanol.
In an alternative embodiment, the mass concentration of the silsesquioxane solution described in step 1 is 5~70%.
In an alternative embodiment, the quality of the silsesquioxane and the phenolic resin in the phenol resin solution
Than being 1:2~99.
In an alternative embodiment, solvent is ethyl alcohol, methanol or isopropanol in the phenol resin solution described in step 2；Step
Phenol resin solution mass concentration described in rapid 2 is 50~85%.
In an alternative embodiment, step 3 is reacted 1-10 hours at 85-120 DEG C first, then heats to 90~180 DEG C
Solidification 2~30 hours.
In an alternative embodiment, 85-120 DEG C is risen to the heating rate of 0.1-3 DEG C/min in step 3；With 0.5-5
DEG C/heating rate of min is warming up to 90~180 DEG C.
The hybrid phenol-formaldehyde resin that silsesquioxane prepared by the above method is modified is applied to thermal-protect ablation material field.
The present invention has the advantages that compared with prior art：
1, the hybrid phenol-formaldehyde resin that silsesquioxane provided in an embodiment of the present invention is modified, shown in formula (1)
POSS molecules react with phenolic resin, are formed with the hybrid phenol-formaldehyde resin cured matter that POSS molecules are chemical crosslinking point, are obtained
Nano-particle enhancing, maximum point of resin starting are played the role of in addition to hybrid phenol-formaldehyde resin, while POSS hybrid molecules
Solution temperature is increased to 580 DEG C or so by 450 DEG C of pure resin, it is residual it is heavy be increased to 65% or so by 58%, significantly improve material
Ablation resistance；
2, in phenolic resin hydridization liquid provided by the invention, the mutual of half cage type POSS molecules and phenolic resin can be realized
It is molten, do not occur being obviously separated, preparation process chemical toxicity is small, cleaning；
3, heating rate is cured by control so that POSS molecules can fully dissolve in phenolic resin as matrix resin, small point
Sub- reaction product, which is fully volatilized, reduces the generation of phenomenon of phase separation；POSS molecules can more occur with phenolic resin as matrix resin simultaneously
Chemical crosslink reaction forms more chemical crosslinking points, increases the intensity and ablation resistance of hybrid resin；
4, the hybrid phenol-formaldehyde resin of half cage type POSS molecular modifications provided by the present invention is in advanced thermally protective materials field
With great application value.
Description of the drawings
Fig. 1：The thermogravimetric analysis of hybrid phenol-formaldehyde resin solidification and pure ba phenolic resin solidfied material prepared by embodiment 1 is bent
Line；
Fig. 2：Scanning electron microscope (SEM) photo in pure ba phenolic resin solidfied material freezing brittle failure face；
Fig. 3：The SEM photograph in the hybrid phenol-formaldehyde resin cured matter freezing brittle failure face prepared by embodiment 1；
Fig. 4：The electron spectroscopy data of POSS and SEM shine in hybrid phenol-formaldehyde resin cured matter brittle failure face prepared by embodiment 1
Piece；
Fig. 5：The thermogravimetric analysis of hybrid phenol-formaldehyde resin solidification and pure high-carbon phenolic resin curing object prepared by embodiment 2 is bent
Line；
Fig. 6：The SEM photograph in the hybrid phenol-formaldehyde resin cured matter freezing brittle failure face prepared by embodiment 2；
Fig. 7：The SEM photograph in hybrid phenol-formaldehyde resin cured matter freezing brittle failure face prepared by embodiment 3.
Specific implementation mode
To facilitate the understanding of the present invention, below in conjunction with Figure of description and specific embodiment to the present invention make more comprehensively,
It meticulously describes, but these embodiments are not construed as being limitation of the present invention, the tool of embodiment offer is provided
Concrete conditions in the establishment of a specific crime, parameter or numerical value could implement the present invention.The method is conventional method unless otherwise instructed.The phenolic aldehyde tree
Fat can utilize existing phenolic resin, or using the phenolic resin of prior art synthesis, half cage type POSS molecules can be from public affairs
Commercial sources acquisition is opened, can also be synthesized according to the prior art, such as document Chemical Reviews, 2010,110:2081-
The 2173 POSS synthetic methods being previously mentioned.
The present invention is described in further detail with reference to specific embodiment.
An embodiment of the present invention provides the hybrid phenol-formaldehyde resins that a kind of silsesquioxane is modified, by silsesquioxane and phenolic aldehyde
Resin cross-linking reaction, wherein the silsesquioxane has the molecular structure as shown in formula (1)：
Wherein, R is isobutyl group, phenyl or iso-octyl, R1For H or
Specifically, in the embodiment of the present invention, the phenolic resin can be phenolic resin cheap and easy to get, boron phenolic
Resin, high-carbon phenolic resin or thermoplastic phenolic resin etc.；
The hybrid phenol-formaldehyde resin that silsesquioxane provided in an embodiment of the present invention is modified, shown in formula (1)
POSS molecules react with phenolic resin, are formed with the hybrid phenol-formaldehyde resin cured matter that POSS molecules are chemical crosslinking point, are obtained
Nano-particle enhancing, maximum point of resin starting are played the role of in addition to hybrid phenol-formaldehyde resin, while POSS hybrid molecules
Solution temperature is increased to 580 DEG C or so by 450 DEG C of pure resin, it is residual it is heavy be increased to 65% or so by 58%, significantly improve material
Ablation resistance.
In an alternative embodiment, the mass ratio of the silsesquioxane and phenolic resin is 1:2-99, preferably 1:4-
20, to ensure that silsesquioxane is evenly dispersed in phenolic resin, while further improving the anti-burning of hybrid phenol-formaldehyde resin
Corrosion.
The embodiment of the present invention additionally provides a kind of preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane is modified, including with
Lower step：
Silsesquioxane is dissolved in alcohols solvent by step 1, obtains silsesquioxane solution；
Step 2, phenol resin solution are added in the silsesquioxane solution, are stirred, obtain hybrid resin liquid；
Step 3, by the hybrid resin liquid at 50~70 DEG C vacuum pump drainage solvent, then elevated cure, obtains sesquialter
Silicone-modified hybrid phenol-formaldehyde resin, wherein the silsesquioxane has following molecular structure：
Wherein, R is isobutyl group, phenyl or iso-octyl, R1For H or
The hybrid phenol-formaldehyde process for preparing resins that silsesquioxane provided in an embodiment of the present invention is modified, by using formula (1)
Shown in POSS molecules react with phenolic resin, formed have with POSS molecules be chemical crosslinking put hybrid phenol-formaldehyde resin
Solidfied material obtains hybrid phenol-formaldehyde resin, and the maximum decomposition temperature of resin starting is increased to 580 DEG C or so by 450 DEG C of pure resin,
It is residual it is heavy be increased to 65% or so by 58%, significantly improve the ablation resistance of material.
In an alternative embodiment, the alcohols solvent described in step 1 is methanol, ethyl alcohol or isopropanol.
In an alternative embodiment, the mass concentration of the silsesquioxane solution described in step 1 is 5~70%.
In an alternative embodiment, in the phenol resin solution described in step 2 solvent be ethyl alcohol, methanol or isopropanol, it is molten
Matter can be phenolic resin cheap and easy to get, boron bakelite resin, high-carbon phenolic resin or thermoplastic phenolic resin etc..
In an alternative embodiment, the phenol resin solution mass concentration described in step 2 is 50~85%.
In an alternative embodiment, the mass ratio of silsesquioxane and phenolic resin described in step 2 is 1:2-99.
In an alternative embodiment, step 3 is reacted 1-10 hours at 85-120 DEG C first, then heats to 90~180 DEG C
Solidification 2~30 hours；It is preferred that rising to 85-120 DEG C with the heating rate of 0.1-3 DEG C/min；With the heating rate of 0.5-5 DEG C/min
It is warming up to 90~180 DEG C.Cure heating rate by control so that POSS molecules can be fully molten in phenolic resin as matrix resin
Solution, small molecule reaction product, which fully volatilizees, reduces the generation of phenomenon of phase separation；Simultaneously POSS molecules can more with phenolic resin
Chemical crosslink reaction occurs for matrix, forms more chemical crosslinking points, increases the intensity and ablation resistance of hybrid resin.
In an alternative embodiment, the hybrid phenol-formaldehyde resin of silsesquioxane modification prepared by the above method is in ablative thermal protection
Application in Material Field.
Embodiment 1
Tri- silanol phenyl POSS molecules of 10g are weighed, are dissolved in 15g alcohol solvents, are stirred until completely molten
Solution is pellucidity, obtains the POSS solution of 40wt% concentration.Weigh the ethyl alcohol for the ba phenolic resin that 120g solid contents are 75%
Solution above-mentioned POSS molecular solution is added in barium novolac solution, at room temperature mechanical agitation 2 hours, until being uniformly mixed, obtains
Hybrid resin liquid.Then phenolic resin hydridization liquid is transferred in vacuum drying oven, 50 DEG C vacuumize half an hour after rise to 55 DEG C of pumpings
Vacuum half an hour, then rise to 60 DEG C and vacuumize 45 minutes or so.The hybrid resin liquid of the complete solvent of pump drainage is poured into mold, is put into
In curing oven, 90 DEG C are risen to from room temperature with the heating rate of 0.5 DEG C/min, 1 hour is kept the temperature, then again with 0.2 DEG C/min's
Heating rate rises to 120 DEG C, and heat preservation rises to 140 DEG C with the rate of 1 DEG C/min again after 4 hours, and after keeping the temperature 2 hours, solidification terminates,
Naturally it is down to room temperature, obtains the hybrid phenol-formaldehyde resin that POSS mass contents are 10%.Attached drawing 1 is that the thermogravimetric of hybrid phenol-formaldehyde resin is bent
Line can be seen that temperature tolerance and ablation resistance are improved, and maximum rhermal decomposition rate temperature is increased to 580 DEG C or so by 460 DEG C,
Carbon yield increases to 66% or so by 59%, and ablation resistance is improved significantly；Attached drawing 2 is the pure barium phenolic aldehyde without POSS molecules
The SEM photograph in resin cured matter brittle failure face, it can be seen that smooth without POSS molecules pure ba phenolic resin solidfied material brittle failure face；It is attached
Fig. 3 is the SEM photograph of hybrid phenol-formaldehyde resin, and as can be seen from the figure POSS molecule aggregates are dispersed in phenolic resin as matrix resin
In；Attached drawing 4 is that the surface-element of ball POSS aggregations in attached drawing 3 analyzes data, it may be determined that ball is POSS molecules, quilt
It is successfully introduced into phenolic resin as matrix resin.
Embodiment 2
Tri- silanol phenyl POSS molecules of 5g are weighed, are dissolved in 15g alcohol solvents, are stirred until being completely dissolved
For pellucidity, the POSS solution of 25wt% concentration is obtained.Weigh the ethyl alcohol for the high-carbon phenolic resin that 136g solid contents are 70%
Solution above-mentioned POSS molecular solution is added in barium novolac solution, at room temperature mechanical agitation 2 hours, until being uniformly mixed, obtains
Hybrid resin liquid.Then phenolic resin hydridization liquid is transferred in vacuum drying oven, 50 DEG C vacuumize half an hour after rise to 55 DEG C of pumpings
Vacuum half an hour, then rise to 60 DEG C and vacuumize 45 minutes or so.The hybrid resin liquid of the complete solvent of pump drainage is poured into mold, is put into
In curing oven, 90 DEG C are risen to from room temperature with the heating rate of 0.5 DEG C/min, 1 hour is kept the temperature, then again with 0.2 DEG C/min's
Heating rate rises to 120 DEG C, and heat preservation rises to 140 DEG C with the rate of 0.5 DEG C/min again after 1 hour, again with 0.5 after keeping the temperature 4 hours
DEG C/rate of min rises to 180 DEG C, 2 hours are kept the temperature, solidification terminates, and is down to room temperature naturally, and it is 5% to obtain POSS mass contents
Hybrid phenol-formaldehyde resin.Attached drawing 5 is that the thermogravimetric curve of hybrid phenol-formaldehyde resin can be seen that temperature tolerance and ablation resistance are improved, most
Big rhermal decomposition rate temperature is increased to 510 DEG C or so by 420 DEG C, and carbon yield increases to 67% or so by 63%, and ablation resistance obtains
To raising；Attached drawing 6 is the SEM photograph of hybrid phenol-formaldehyde resin, and as can be seen from the figure POSS molecule aggregates are dispersed in phenol
In urea formaldehyde matrix.
Embodiment 3
Tri- silanol phenyl POSS molecules of 5g are weighed, are dissolved in 15g alcohol solvents, are stirred until being completely dissolved
For pellucidity, it is configured to the POSS solution of 25wt% concentration.Weigh the ethyl alcohol for the ba phenolic resin that 130g solid contents are 75%
Solution above-mentioned POSS molecular solution is added in barium novolac solution, at room temperature mechanical agitation 2 hours, until being uniformly mixed.Then
Phenolic resin hydridization liquid is transferred in vacuum drying oven, 50 DEG C vacuumize and rise to 55 DEG C after half an hour and vacuumize half an hour, then rise
It is vacuumized 45 minutes or so to 60 DEG C.The hybrid resin liquid of the complete solvent of pump drainage is poured into mold, is put into curing oven, with
The heating rate of 0.5 DEG C/min rises to 90 DEG C from room temperature, keeps the temperature 1 hour, is then risen to again with the heating rate of 0.2 DEG C/min
120 DEG C, heat preservation rises to 140 DEG C with the rate of 1 DEG C/min again after 4 hours, and after keeping the temperature 2 hours, solidification terminates, and is down to room naturally
Temperature obtains the hybrid phenol-formaldehyde resin that POSS mass contents are 5%.Attached drawing 7 is the SEM photograph of hybrid phenol-formaldehyde resin, can from figure
To find out that POSS molecule aggregates are dispersed in phenolic resin as matrix resin.POSS molecules it is evenly dispersed, be conducive to improve miscellaneous
Change the mechanical strength and ablation carburization zone intensity of phenolic resin
Embodiment 4
Tri- silanol phenyl POSS molecules of 10g are weighed, are dissolved in 90g alcohol solvents, are stirred until completely molten
Solution is pellucidity, is configured to the POSS solution of 10wt% concentration.Weigh the boron modified phenolic resin that 20g solid contents are 65%
Ethanol solution above-mentioned POSS molecular solution is added in barium novolac solution, at room temperature mechanical agitation 1 hour, until being uniformly mixed.
Then phenolic resin hydridization liquid is transferred in vacuum drying oven, 50 DEG C vacuumize and rise to 55 DEG C after half an hour and vacuumize half an hour,
60 DEG C are risen to again to vacuumize 30 minutes or so.The hybrid resin liquid of the complete solvent of pump drainage is poured into mold, is put into curing oven,
90 DEG C are risen to from room temperature with the heating rate of 0.5 DEG C/min, 1 hour is kept the temperature, is then risen to again with the heating rate of 0.2 DEG C/min
120 DEG C, heat preservation rises to 140 DEG C with the rate of 1 DEG C/min again after 4 hours, and after keeping the temperature 2 hours, solidification terminates, and is down to room naturally
Temperature obtains the hybrid phenol-formaldehyde resin that POSS mass contents are about 45%.Thermogravimetric analysis data shows the maximum heat point of hybrid resin
Solution rate temperature is increased to 621 DEG C or so by 450 DEG C, and carbon yield increases to 77% or so by 60%, and ablation resistance obtains significantly
Ground is promoted.
Embodiment 5
Tri- silanol isobutyl group POSS molecules of 10g are weighed, are dissolved in 30g alcohol solvents, are stirred until completely
It is dissolved as pellucidity, is configured to the POSS solution of 25wt% concentration.The solution of 40g Resol A rank phenolic resin is weighed, Gu
Content is 80%.Above-mentioned POSS molecular solution is added in barium novolac solution, at room temperature mechanical agitation half an hour, until mixing is equal
It is even.Then phenolic resin hydridization liquid is transferred in vacuum drying oven, 50 DEG C vacuumize and rise to 55 DEG C after half an hour to vacuumize half small
When.The hybrid resin liquid of the complete solvent of pump drainage is poured into mold, is put into curing oven, with the heating rate of 0.5 DEG C/min from
Room temperature rises to 90 DEG C, keeps the temperature 1 hour, then rises to 120 DEG C again with the heating rate of 0.1 DEG C/min, heat preservation cures knot after 4 hours
Beam is down to room temperature naturally, obtains the hybrid phenol-formaldehyde resin that POSS mass contents are about 24%.Thermogravimetric analysis data shows hydridization
The maximum rhermal decomposition rate temperature of resin is increased to 580 DEG C or so by 430 DEG C, and carbon yield increases to 62% or so by 56%, resistance to
It is ablative to be improved.
Embodiment 6
5g triphen sulphenyl POSS molecules are weighed, are dissolved in 20g alcohol solvents, are stirred until completely molten
Solution is pellucidity, is configured to the POSS solution of 20wt% concentration.The solution of 20g Resol A rank phenolic resin is weighed, admittedly contain
Amount is 80%.Above-mentioned POSS molecular solution is added in barium novolac solution, at room temperature mechanical agitation half an hour, until mixing is equal
It is even.Then phenolic resin hydridization liquid is transferred in vacuum drying oven, 50 DEG C vacuumize and rise to 55 DEG C after half an hour to vacuumize half small
When.The hybrid resin liquid of the complete solvent of pump drainage is poured into mold, is put into curing oven, with the heating rate of 0.5 DEG C/min from
Room temperature rises to 90 DEG C, keeps the temperature 1 hour, then rises to 120 DEG C again with the heating rate of 0.1 DEG C/min, heat preservation cures knot after 4 hours
Beam is down to room temperature naturally, obtains the hybrid phenol-formaldehyde resin that POSS mass contents are about 25%.Thermogravimetric analysis data shows hydridization
The maximum rhermal decomposition rate temperature of resin is increased to 615 DEG C or so by 430 DEG C, and carbon yield increases to 68% or so by 57%, resistance to
It is ablative to be significantly improved.
The above, best specific implementation mode only of the invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.
The content that description in the present invention is not described in detail belongs to the known technology of professional and technical personnel in the field.
Claims (10)
1. the hybrid phenol-formaldehyde resin that a kind of silsesquioxane is modified, which is characterized in that be crosslinked by silsesquioxane and phenolic resin
Reaction is made, and the silsesquioxane has following molecular structure：
Wherein, R is isobutyl group, phenyl or iso-octyl, R1For H or
2. the hybrid phenol-formaldehyde resin that silsesquioxane according to claim 1 is modified, which is characterized in that the sesquialter silicon
The mass ratio of oxygen alkane and phenolic resin is 1:2~99.
3. a kind of preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane is modified, which is characterized in that include the following steps：
Step 1：Silsesquioxane is dissolved in alcohols solvent, silsesquioxane solution is obtained；
Step 2：The silsesquioxane solution is mixed with phenol resin solution, is stirred evenly, hybrid resin liquid is obtained；
Step 3, by the hybrid resin liquid at 50~70 DEG C vacuum pump drainage solvent, then elevated cure, obtains silsesquioxane
The hybrid phenol-formaldehyde resin that alkane is modified.
4. the preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane according to claim 3 is modified, which is characterized in that step
Alcohols solvent described in rapid 1 is methanol, ethyl alcohol or isopropanol.
5. the preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane according to claim 3 or 4 is modified, feature exist
In the mass concentration of the silsesquioxane solution described in step 1 is 5~70%.
6. the preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane according to claim 3 is modified, which is characterized in that institute
The mass ratio of the silsesquioxane stated and the phenolic resin in the phenol resin solution is 1:2~99.
7. the preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane according to claim 3 is modified, which is characterized in that step
Solvent is ethyl alcohol, methanol or isopropanol in phenol resin solution described in rapid 2；Phenol resin solution quality described in step 2 is dense
Degree is 50~85%.
8. the preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane according to claim 3 is modified, which is characterized in that step
Rapid 3 react 1-10 hours at 85-120 DEG C first, then heat to 90~180 DEG C and cure 2~30 hours.
9. the preparation method for the hybrid phenol-formaldehyde resin that silsesquioxane according to claim 8 is modified, which is characterized in that step
In rapid 3 85-120 DEG C is risen to the heating rate of 0.1-3 DEG C/min；It is warming up to 90~180 with the heating rate of 0.5-5 DEG C/min
℃。
10. the hybrid phenol-formaldehyde resin being modified by silsesquioxane prepared by any one of claim 3-9 the methods is applied to burn
Lose heat insulation material field.
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| CN110526736A (en) * | 2019-10-09 | 2019-12-03 | 华东理工大学 | A kind of anti-oxidant nano-pore structure carbon composite and preparation method thereof |
| CN112143169A (en) * | 2020-06-30 | 2020-12-29 | 西北工业大学 | High-silica fiber reinforced reactive silsesquioxane modified hybrid phenolic composite material and preparation method thereof |
| CN112175231A (en) * | 2020-09-30 | 2021-01-05 | 航天材料及工艺研究所 | Phenolic toughening modified porous hybrid silicon resin, preparation method and application |
| CN112210079A (en) * | 2020-10-23 | 2021-01-12 | 中国科学院化学研究所 | Silicon hybrid phenolic resin and synthetic method thereof |
| CN114835903A (en) * | 2022-04-28 | 2022-08-02 | 北京理工大学 | Boron-containing silsesquioxane, preparation method thereof, modified phenolic resin, preparation method and application thereof |
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| CN110526736A (en) * | 2019-10-09 | 2019-12-03 | 华东理工大学 | A kind of anti-oxidant nano-pore structure carbon composite and preparation method thereof |
| CN112143169A (en) * | 2020-06-30 | 2020-12-29 | 西北工业大学 | High-silica fiber reinforced reactive silsesquioxane modified hybrid phenolic composite material and preparation method thereof |
| CN112175231A (en) * | 2020-09-30 | 2021-01-05 | 航天材料及工艺研究所 | Phenolic toughening modified porous hybrid silicon resin, preparation method and application |
| CN112210079A (en) * | 2020-10-23 | 2021-01-12 | 中国科学院化学研究所 | Silicon hybrid phenolic resin and synthetic method thereof |
| CN114835903A (en) * | 2022-04-28 | 2022-08-02 | 北京理工大学 | Boron-containing silsesquioxane, preparation method thereof, modified phenolic resin, preparation method and application thereof |
| CN114835903B (en) * | 2022-04-28 | 2023-03-14 | 北京理工大学 | Boron-containing silsesquioxane and preparation method thereof, modified phenolic resin and preparation method and application thereof |
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