CN105885313A - Resin crosslinking polyvinyl alcohol type aerogel and preparation method and application of resin crosslinking polyvinyl alcohol type aerogel - Google Patents
Resin crosslinking polyvinyl alcohol type aerogel and preparation method and application of resin crosslinking polyvinyl alcohol type aerogel Download PDFInfo
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- CN105885313A CN105885313A CN201610263902.3A CN201610263902A CN105885313A CN 105885313 A CN105885313 A CN 105885313A CN 201610263902 A CN201610263902 A CN 201610263902A CN 105885313 A CN105885313 A CN 105885313A
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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
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
- C08J2461/10—Phenol-formaldehyde condensates
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08J2461/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2461/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses resin crosslinking polyvinyl alcohol type aerogel and a preparation method and application of the resin crosslinking polyvinyl alcohol type aerogel. The resin crosslinking polyvinyl alcohol type aerogel is obtained by blending a synthetic resin precursor solution and aqueous polyvinyl alcohol, subjecting a blend to freeze drying to obtain aerogel and subjecting the aerogel to cross-linking curing. The density of the resin crosslinking polyvinyl alcohol type aerogel is 76-179 Kg/m<3>, limit oxygen index is 23.0-38.5%, peak heat release rate is 48.0-292.1 kW/m<2>, compression modulus is 7.2-37.2 MPa, and water contact angle is 33.1-136.2 degrees. The resin crosslinking polyvinyl alcohol type aerogel prepared from raw materials shows a regular and uniform three-dimensional network structure and better mechanical and flame-retardant properties, avoids negative effects caused by holes due to adding a fire retardant and other substances into the aerogel, solves the problem of water absorption of existing aerogel materials and can be widely applied to the fields of construction insulation, piping insulation, sound insulation and the like owing to excellent inherent thermal insulation and sound insulation properties.
Description
Technical field
The invention belongs to aerogel material and preparing technical field thereof, be specifically related to a kind of resin crosslinks polyvinyl alcohol aeroge and
Its preparation method and application.
Background technology
Energy shortage problem has become as the significant problem affecting world today's development, and energy-saving and cost-reducing is to alleviate energy shortage
Important Action, our country is particularly important by this.
Domestic market mainly use foam concrete, diatomite product, silicate heat-protective coatings, ceramic thermal insulation material,
Glue powder polyphenyl particle, polystyrene block (EPS), extruded sheet (XPS) and polyurethane etc. are as insulation material.Wherein, EPS,
Although the organic insulation material such as XPS and polyurethane is because having the features such as little, the high insulating effect of density, lead at insulation material
Territory occupies leading position, but, but there is the critical defects such as inflammable, toxicity is big in these organic insulation materials so that by it
The fire caused emerges in an endless stream, the safety of life and property of serious harm people.And the nothing such as foam concrete, diatomite product
Machine insulation material, though nontoxic and good flame resistance, but there is again certain defect at the aspect such as density and heat insulation effect.
Aeroge is a kind of new material with tridimensional network, and it has, and density is low, porosity is high, aperture is little, ratio
Surface area is big and the feature such as high insulating effect, is the solid material that current heat conductivity is minimum, density is minimum, is also tradition
The ideal substitute of insulation material, receives the extensive concern of people.For the research of aerogel material the most deep be inorganic
Aerogel material, particularly silica aerogel material, but owing to its preparation condition is harsh, it is generally required to use super facing
The method that boundary is dried, hardly results in extensively application, only applies in the high-end field such as Aero-Space, military project.Meanwhile, titanium dioxide
Silica aerogel there is also the shortcomings such as frangible.Organic aerogel material then exist raw material costly, toxicity relatively big, and have
There are the shortcomings such as inflammable.Therefore, organic/inorganic composite aerogel arises at the historic moment, and has organic aerogel and inorganic gas because of it simultaneously
The advantage of gel, can make up its defect being individually present to a certain extent.
As United States Patent (USP) US3203903 reports the preparation method of a kind of polyalcohol/clay soil aeroge, the method is by simply
Polymer and inorganic clay are blended after carry out lyophilization, be prepared for the organic/inorganic composite aerogel of stable physical property
Material.Although the method is environmentally friendly, price is the cheapest, and overcome some tradition inorganic aerogels and organic gas
Defect in gel preparation course, but, it yet suffers from some problems: firstly, since the polymer that the method is used
Being water-soluble polymer, its preparation process is again simple physical blending, and products therefrom can exist absorptive problem undoubtedly,
And this mechanical performance that will have a strong impact on aeroge and heat-insulating property；Secondly, the mechanical performance of clay-type substance own is poor,
Even if with polymer is blended, the aeroge intensity of preparation is the least, it is difficult to reach the requirement of application；3rd, due to the party
Raw material required for method preparation remains based on Organic substance, and its fire resistance must also be its obstacle being difficult to overcome.
And for example the patent of invention of Patent No. 2013310043651.4 discloses a kind of inorganic micro-and nano-particles aeroge/polymer
Building heat preservation aerogel material and preparation method.The preparation method that the above-mentioned United States Patent (USP) of this patent utilization is similar, is joined by regulation
Side is prepared for the organic/inorganic aerogel composite of high flame retardant, high heat insulating ability.Although the method solves to a certain extent
Fire-retardant problem, but because needs add substantial amounts of inorganic matter, inorganic content is even up to ten times of content of organics,
Thus it is not the most fine for making its molding, density and durability.If Organic substance and inorganic content are reduced simultaneously, density
Although can reduce, but its mechanical performance is poor.Simultaneously as the raw material that this patent is used is hydrophilic, therefore
The problem that this aerogel material certainly exists water suction.
It addition, also have some researchs that above-mentioned patent is improved, add some efficient flame-retarding agents, such as APP
(Wang L.et al.Materials and Design 2013,52,609-614), piperazine ammonium polyphosphate modifying (Wang Y.T.et al.
ACS Appl.Mater.Interfaces 2015,7,1780-1786) etc..Owing to this based flame retardant exists deliquescent problem,
The tridimensional network of meeting heavy damage aerogel material, thus greatly reduce the mechanical performance of material.And for example application number
Be 201410853578.1 the modified APP of patent of invention piperazine replace APP as fire retardant polymer
Aeroge, although can to a certain degree improve its mechanical performance.But, the APP of piperazine modification is three-dimensional for aeroge
Cancellated destruction is still obvious, the biggest hence for aerogel material mechanical impact.Meanwhile, the method is the most not
Mention the problem in terms of the water absorption how solving material, and the modified APP of piperazine and the Organic substance of addition itself
All there is the characteristic of water suction, thus the problem that this aerogel material yet suffers from water suction can be speculated.
Summary of the invention
The problem that it is an object of the invention to exist for prior art, first provides a kind of resin crosslinks polyvinyl alcohol aeroge
Preparation method, the method is with polyvinyl alcohol as base material, and resin precursor is cross-linking agent, prepares by controlling process conditions
The degree of cross linking is controlled, molding simply, do not shrink, and can also have excellent fire-retardancy, mechanical performance and hydrophobic performance simultaneously
Aeroge.
It is a further object of the present invention to provide a kind of resin crosslinks polyvinyl alcohol aeroge prepared by said method.
Another object of the present invention is to provide the application of resin crosslinks polyvinyl alcohol aeroge.
The preparation method of the resin crosslinks polyvinyl alcohol aeroge that the present invention provides, processing step and the condition of the method are as follows:
(1) first by use the synthetic resin precursor solution prepared of prior art and mass percent concentration be 1～10% poly-
Glycohol solution is 1:0.2～10 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system to 1～7, then at
-5～-196 DEG C at freezing be solid, continue after be vacuum dried again i.e. to prepare at-80～40 DEG C and mix and have the polyethylene of resin precursor
Alcohol aeroge；
(2) by (1st) step gained aeroge crosslinking curing 1～60h at 60～150 DEG C, resin crosslinks polyethylene is i.e. prepared
Alcohol aeroge.
Synthetic resin precursor solution used in above method and poly-vinyl alcohol solution are according to hydroxyl mol ratio preferred 1:0.5～5.
Synthetic resin precursor solution used in above method is Lauxite precursor solution, novolak resin precursor liquid solution
Or any one in melmac precursor solution.
The mass percent concentration preferably 2～8% of poly-vinyl alcohol solution used in above method.
System pH described in above method is preferably adjusted to 4～7；Described lyophilization temperature preferably-50～25 DEG C；Described
The temperature preferably 80～120 DEG C of crosslinking curing；The described crosslinking curing time preferably 12～48h.
Prior art described in above method be Patent No. 92107343.7,201210389987.1,201010122554.0,
201110128180.8 patent of invention and document: Guan Chang etc. chemical intermediate .2004,7:36-39；Zhang X.F.et al.
Method disclosed in Pigment and Resin Technology 2014,43,69-74.Use the synthesis used by the preparation of these methods
Response time during resin precursor solution preferably 30～60min.
The resin crosslinks polyvinyl alcohol aeroge prepared by said method that the present invention provides, this aeroge is to be with polyvinyl alcohol
Base material is blended with synthetic resin precursor solution, freezing, crosslinking preparation, and its density is 76～179Kg/m3, the limit
Oxygen index (OI) is 23.0～38.5%, and peak heat rate of release is 48.0～292.1kW/m2, modulus of compressibility is 7.2～37.2MPa, water
Contact angle is 33.1～136.2 °.
When the mass percent concentration of polyvinyl alcohol preferably 2～8% in above aeroge, synthetic resin precursor solution and polyethylene
When alcoholic solution is preferably 1:0.5～5 according to hydroxyl mol ratio, the density of this material is 76～179Kg/m3, limited oxygen index is preferred
Being 26.4～37.9%, peak heat rate of release is 55.9～160.6kW/m2, modulus of compressibility is 12.2～37.2MPa, water contact angle
It is preferably 76.3～135.9 °.
The application of the above-mentioned resin crosslinks polyvinyl alcohol aeroge that the present invention provides is to lead in building heat preservation, pipe insulation and sound insulation
Application in territory.
Compared with prior art, the invention have the advantages that
1, synthetic resin presoma is simply joined PVA-based by the aerogel material provided due to the present invention as cross-linking agent
Prepared by material, there is no the addition of other materials, as fire retardant or reinforcing agent add, thus after system reaction completely
Formed is an a kind of aerogel material purely of complete entirety, and by its microstructure observing is found, should
What material not only presented is the tridimensional network of a kind of regular uniform, has more preferable heat-insulating property, and avoids existing skill
That brings because adding aerogel particle or add fire retardant and other materials generation hole in aeroge in art is negative
Impact, including the disadvantage such as heat-insulating property reducing material.
2, the aerogel material provided due to the present invention is first to mix in water with the water-soluble compound of both of which, then leads to
Cross cross-linking reaction to be prepared from, thus prior art addition inorganic nano-particle or efficient flame-retarding agent both can have been avoided to be brought
Dispersion and the problem of reduction aerogel material mechanical performance, again without the pollution problem using organic solvent to be brought.
3, gas is formed owing to synthetic resin contained in the aerogel material of present invention offer both can become cross-linking agent with polyvinyl alcohol
The tridimensional network of gel rubber material, can be again that aerogel material provides excellent anti-flammability, thus not only increase material
Mechanical performance, moreover it is possible to improve the fire resistance of material, the most also can avoid because improving more brought being difficult to of additive content
The problem of molding.
4, the aerogel material provided due to the present invention is prepared by crosslinking completely, does not add some other additive,
And contained hydrophilic group after cross-linking, can be made in raw material to disappear, thus the hydrophobicity of material and resistance to can be improved to a certain extent
Aqueous, solves the water absorption issue that existing aerogel material exists.
5, the aerogel material provided due to the present invention has fire resistance, hydrophobic performance and the mechanical performance of excellence simultaneously, adds
The heat-insulating property of the excellence that upper aerogel material is intrinsic and sound insulation value, it is in fields such as building heat preservation, pipe insulation, sound insulations
There is application prospect widely.
6, the preparation method that the present invention provides is simple, ripe, it is easy to popularization and application.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the melamine resin cross-linking polyvinyl alcohol aeroge of the embodiment of the present invention 3 preparation.
Polyvinyl alcohol and melamine resin have built the skeleton of aeroge after cross-linking as seen from the figure, define uniform three
Dimension network structure.
Fig. 2 is the scanning electron microscope (SEM) photograph of the phenolic resin cross-linking polyvinyl alcohol aeroge of the embodiment of the present invention 14 preparation.Can from figure
Build the skeleton of aeroge after seeing polyvinyl alcohol and phenolic resin crosslinking, define uniform tridimensional network.
Fig. 3 is the water contact angle test of the melamine resin cross-linking polyvinyl alcohol aeroge of the embodiment of the present invention 3 preparation
Image.The aerogel material that as seen from the figure prepared by the present invention, after crosslinking, is provided with certain hydrophobicity.
Fig. 4 is the water contact angle test image of the phenolic resin cross-linking polyvinyl alcohol aeroge of the embodiment of the present invention 14 preparation.From
The aerogel material that in figure prepared by the visible present invention, after crosslinking, is provided with certain hydrophobicity.
Fig. 5 is the electronic photo of the melamine resin cross-linking polyvinyl alcohol aeroge of the embodiment of the present invention 3 preparation.From
The aerogel material shape that in photo prepared by the visible present invention is regular, the phenomenons such as contraction does not occur.
Fig. 6 is that the melamine resin cross-linking polyvinyl alcohol aeroge of the embodiment of the present invention 3 preparation dissolves in 90 DEG C of water
After 12h, the electronic photo of (b) after not drying (a) and drying.The airsetting prepared from the present invention seen from two photo comparison
Glue material will not dissolve in the hot water, and dried sample keeps original appearance substantially, shows the water resistance of excellence.
Detailed description of the invention
Embodiment is given below so that the present invention to be specifically described, it is necessary to it is pointed out here that to be that following example are served only for right
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, and the person skilled in the art in this field can
The present invention made some nonessential improvement and adjustment according to present invention.
What deserves to be explained is, the density of the aerogel material prepared by following example and comparative example is according to GB/T
6343-2009 test；Limited oxygen index is tested according to ASTM D 2863-2009；HRR is then logical
Cross taper calorimetric to test at 50kW/m2Under heat radiation power, test obtains；Modulus of compressibility is according to ASTM D
1621-2010 carries out testing；Water contact angle test is that the water droplet of 3 microlitres drops in aerogel material table prepared by the present invention
Carrying out after the 10s of face shooting, each sample carries out 5 tests, averages and is water contact angle numerical value；In order to further
Test material water resistance, devise dissolvings-be dried experiment, first material is put in 90 DEG C of water dissolve 12h, observe molten
Solution situation, after taking-up, vacuum drying, observe contraction situation.
Embodiment 1
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 30min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 1% be 1:0.2 mix homogeneously according to hydroxyl mol ratio, then the pH of system is adjusted
Joint, to 1, pours mould into, and at-5 DEG C, freezing is solid, continue after at-80 DEG C, be vacuum dried again i.e. prepared mixing have resin
The polyvinyl alcohol aeroge of presoma；By prepared aeroge crosslinking curing 60h at 60 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 2
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 40min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 2% be 1:0.5 mix homogeneously according to hydroxyl mol ratio, then the pH of system is adjusted
Joint, to 4, pours mould into, and at-50 DEG C, freezing is solid, continue after at-50 DEG C, be vacuum dried again i.e. prepared mixing have resin
The polyvinyl alcohol aeroge of presoma；By prepared aeroge crosslinking curing 48h at 80 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 3
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 50min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 5% be 1:1 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system
To 5, pouring mould into, at-80 DEG C, freezing is solid, continue after be vacuum dried at-20 DEG C again and i.e. prepare and mix and have resin before
Drive the polyvinyl alcohol aeroge of body；By prepared aeroge crosslinking curing 36h at 90 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 4
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 60min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 8% be 1:2 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system
To 6, pouring mould into, at-100 DEG C, freezing is solid, continue after be vacuum dried again i.e. to prepare at-10 DEG C and mix and have resin
The polyvinyl alcohol aeroge of presoma；By prepared aeroge crosslinking curing 24h at 100 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 5
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 30min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 10% be 1:10 mix homogeneously according to hydroxyl mol ratio, then the pH of system is adjusted
Joint, to 2, pours mould into, and at-30 DEG C, freezing is solid, continue after at 40 DEG C, be vacuum dried again i.e. prepared mixing have resin
The polyvinyl alcohol aeroge of presoma；By prepared aeroge crosslinking curing 1h at 150 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 6
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 30min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 8% be 1:1 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system
To 7, pouring mould into, at-100 DEG C, freezing is solid, continue after be vacuum dried at 0 DEG C again and i.e. prepare and mix and have resin before
Drive the polyvinyl alcohol aeroge of body；By prepared aeroge crosslinking curing 18h at 120 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 7
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 40min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 5% be 1:1 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system
To 6, pouring mould into, at-80 DEG C, freezing is solid, continue after be vacuum dried at 10 DEG C again and i.e. prepare and mix and have resin before
Drive the polyvinyl alcohol aeroge of body；By prepared aeroge crosslinking curing 12h at 110 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 8
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 50min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 5% be 1:0.5 mix homogeneously according to hydroxyl mol ratio, then the pH of system is adjusted
Joint, to 5, pours mould into, and at-50 DEG C, freezing is solid, continue after at 25 DEG C, be vacuum dried again i.e. prepared mixing have resin
The polyvinyl alcohol aeroge of presoma；By prepared aeroge crosslinking curing 24h at 100 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 9
After first tripolycyanamide and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, anti-in 80 DEG C
Answer 60min, prepare melamine resin precursor solution；By this melamine resin precursor solution and quality
Percent concentration be the poly-vinyl alcohol solution of 5% be 1:2 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system
To 4, pouring mould into, at-50 DEG C, freezing is solid, continue after be vacuum dried at 25 DEG C again and i.e. prepare and mix and have resin before
Drive the polyvinyl alcohol aeroge of body；By prepared aeroge crosslinking curing 48h at 90 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 10
After first carbamide and formaldehyde being mixed according to the stirring of mol ratio 1:2 and the pH of its system is adjusted to 8.0, in 80 DEG C of reactions
30min, prepares Lauxite precursor solution；By this Lauxite precursor solution and mass percent concentration be 1% poly-
Glycohol solution is 1:0.2 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system to 1, pours mould into, then
At-20 DEG C, freezing is solid, continue after be vacuum dried again i.e. to prepare at-40 DEG C and mix and have the polyvinyl alcohol gas of resin precursor
Gel；By prepared aeroge crosslinking curing 54h at 70 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 11
After first carbamide and formaldehyde being mixed according to the stirring of mol ratio 1:2 and the pH of its system is adjusted to 8.0, in 80 DEG C of reactions
40min, prepares Lauxite precursor solution；By this Lauxite precursor solution and mass percent concentration be 5% poly-
Glycohol solution is 1:1 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system to 4, pours mould into, then at
At-80 DEG C, freezing is solid, continue after be vacuum dried again i.e. to prepare at 0 DEG C and mix and have the polyvinyl alcohol aeroge of resin precursor；
By prepared aeroge crosslinking curing 24h at 80 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 12
After first carbamide and formaldehyde being mixed according to the stirring of mol ratio 1:2 and the pH of its system is adjusted to 8.0, in 80 DEG C of reactions
50min, prepares Lauxite precursor solution；By this Lauxite precursor solution and mass percent concentration be 8% poly-
Glycohol solution is 1:5 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system to 5, pours mould into, then at
At-100 DEG C, freezing is solid, continue after be vacuum dried again i.e. to prepare at-10 DEG C and mix and have the polyvinyl alcohol airsetting of resin precursor
Glue；By prepared aeroge crosslinking curing 48h at 90 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 13
After first phenol and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, in 80 DEG C of reactions
40min, prepares novolak resin precursor liquid solution；By this novolak resin precursor liquid solution and mass percent concentration be 2% poly-
Glycohol solution is 1:0.5 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system to 6, pours mould into, then
At-196 DEG C, freezing is solid, continue after be vacuum dried again i.e. to prepare at-20 DEG C and mix and have the polyvinyl alcohol gas of resin precursor
Gel；By prepared aeroge crosslinking curing 48h at 100 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 14
After first phenol and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, in 80 DEG C of reactions
50min, prepares novolak resin precursor liquid solution；By this novolak resin precursor liquid solution and mass percent concentration be 5% poly-
Glycohol solution is 1:1 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system to 7, pours mould into, then at
At-80 DEG C, freezing is solid, continue after be vacuum dried again i.e. to prepare at-50 DEG C and mix and have the polyvinyl alcohol airsetting of resin precursor
Glue；By prepared aeroge crosslinking curing 24h at 120 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Embodiment 15
After first phenol and formaldehyde being mixed according to the stirring of mol ratio 1:3 and the pH of its system is adjusted to 8.5, in 80 DEG C of reactions
60min, prepares novolak resin precursor liquid solution；It is 10% by this novolak resin precursor liquid solution and mass percent concentration
Poly-vinyl alcohol solution is 1:10 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system to 3, pours mould into,
At-40 DEG C, freezing is solid, continue after be vacuum dried again i.e. to prepare at-80 DEG C and mix and have the polyvinyl alcohol of resin precursor
Aeroge；By prepared aeroge crosslinking curing 1h at 60 DEG C.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Comparative example
Pouring the poly-vinyl alcohol solution that mass percent concentration is 5% into mould, at-80 DEG C, freezing is solid, more again in
Be vacuum dried at-20 DEG C, continue after prepared aeroge dried at 80 DEG C 24h.
The density of gained aerogel material, oxygen index (OI), peak heat rate of release, modulus of compressibility, water contact angle, put into 90 DEG C
In water, the test result such as the dissolving situation of 12h and vacuum drying after-contraction situation sees attached list.
Table
Claims (10)
1. a preparation method for resin crosslinks polyvinyl alcohol aeroge, processing step and the condition of the method are as follows:
(1) the synthetic resin precursor solution first employing prior art prepared is 1～10% with mass percent concentration
Poly-vinyl alcohol solution be 1:0.2～10 mix homogeneously according to hydroxyl mol ratio, then by the pH regulator of system to 1～7,
At-5～-196 DEG C, freezing is solid, continue after be vacuum dried again i.e. to prepare at-80～40 DEG C and mix and have resin forerunner
The polyvinyl alcohol aeroge of body；
(2) by (1st) step gained aeroge crosslinking curing 1～60h at 60～150 DEG C, resin crosslinks is i.e. prepared
Polyvinyl alcohol aeroge.
The preparation method of resin crosslinks polyvinyl alcohol aeroge the most according to claim 1, used in the method
Synthetic resin precursor solution and poly-vinyl alcohol solution be 1:0.5～5 according to hydroxyl mol ratio.
The preparation method of resin crosslinks polyvinyl alcohol aeroge the most according to claim 1 and 2, in the method
Synthetic resin precursor solution used is Lauxite precursor solution, novolak resin precursor liquid solution or melamine
Any one in polyimide resin precursor solution；The mass percent concentration of polyvinyl alcohol used is 2～8%.
The preparation method of resin crosslinks polyvinyl alcohol aeroge the most according to claim 1 and 2, in the method
Described system pH regulator is to 4～7；Described vacuum drying temperature is-50～25 DEG C.
The preparation method of resin crosslinks polyvinyl alcohol aeroge the most according to claim 3, described in the method
System pH regulator to 4～7；Described vacuum drying temperature is-50～25 DEG C.
The preparation method of resin crosslinks polyvinyl alcohol aeroge the most according to claim 1 and 2, in the method
The temperature of described crosslinking curing is 80～120 DEG C；The described crosslinking curing time is 12～48h.
The preparation method of resin crosslinks polyvinyl alcohol aeroge the most according to claim 3, described in the method
The temperature of crosslinking curing be 80～120 DEG C；The described crosslinking curing time is 12～48h.
The preparation method of resin crosslinks polyvinyl alcohol aeroge the most according to claim 5, described in the method
The temperature of crosslinking curing be 80～120 DEG C；The described crosslinking curing time is 12～48h.
9. the resin crosslinks polyvinyl alcohol aeroge prepared by method described in claim 1, this aeroge be with
Polyvinyl alcohol is base material blended with synthetic resin precursor solution, freezing, crosslinking preparation, and its density is
76～179Kg/m3, limited oxygen index is 23.0～38.5%, and peak heat rate of release is 48.0～292.1kW/m2, pressure
Contracting modulus is 7.2～37.2MPa, and water contact angle is 33.1～136.2 °.
10. one kind by resin crosslinks polyvinyl alcohol aeroge according to claim 9 at building heat preservation, pipeline
Application in insulation and soundproofing field.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903434A (en) * | 2017-11-22 | 2018-04-13 | 四川大学 | A kind of anisotropy polyvinyl alcohol aerogel material and preparation method thereof |
| CN108047485A (en) * | 2017-12-13 | 2018-05-18 | 西华大学 | Aerogel material and preparation method thereof |
| CN109485910A (en) * | 2018-11-30 | 2019-03-19 | 四川大学 | Flexible high-resistance combustion property biology base aerogel material and preparation method thereof |
| CN113716548A (en) * | 2021-10-13 | 2021-11-30 | 天津晨祥丰凯新材料科技有限公司 | Preparation method of carbon aerogel and precursor thereof |
| CN116655998A (en) * | 2023-06-07 | 2023-08-29 | 西华大学 | Method for preparing melamine formaldehyde resin aerogel by normal pressure drying |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085579A (en) * | 1993-10-12 | 1994-04-20 | 刘永浩 | New waterproof polyvinyl alcohol composite material (alkene ester matrix material) and method for making and purposes |
| CN102786642A (en) * | 2012-08-10 | 2012-11-21 | 南京林业大学 | Nanometer cellulose/polyvinyl alcohol gel composite material |
| CN102827442A (en) * | 2012-08-29 | 2012-12-19 | 华南理工大学 | Method for preparing polyvinyl alcohol and polyurethane super absorbent sponge |
| CN103599734A (en) * | 2013-11-22 | 2014-02-26 | 中国工程物理研究院核物理与化学研究所 | Aerogel material and preparation method thereof |
| CN104592697A (en) * | 2014-12-31 | 2015-05-06 | 四川大学 | Low-density and high-flame-retardant composite porous material and preparation method and application thereof |
-
2016
- 2016-04-26 CN CN201610263902.3A patent/CN105885313B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085579A (en) * | 1993-10-12 | 1994-04-20 | 刘永浩 | New waterproof polyvinyl alcohol composite material (alkene ester matrix material) and method for making and purposes |
| CN102786642A (en) * | 2012-08-10 | 2012-11-21 | 南京林业大学 | Nanometer cellulose/polyvinyl alcohol gel composite material |
| CN102827442A (en) * | 2012-08-29 | 2012-12-19 | 华南理工大学 | Method for preparing polyvinyl alcohol and polyurethane super absorbent sponge |
| CN103599734A (en) * | 2013-11-22 | 2014-02-26 | 中国工程物理研究院核物理与化学研究所 | Aerogel material and preparation method thereof |
| CN104592697A (en) * | 2014-12-31 | 2015-05-06 | 四川大学 | Low-density and high-flame-retardant composite porous material and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903434A (en) * | 2017-11-22 | 2018-04-13 | 四川大学 | A kind of anisotropy polyvinyl alcohol aerogel material and preparation method thereof |
| CN107903434B (en) * | 2017-11-22 | 2023-03-31 | 四川大学 | Anisotropic polyvinyl alcohol aerogel material and preparation method thereof |
| CN108047485A (en) * | 2017-12-13 | 2018-05-18 | 西华大学 | Aerogel material and preparation method thereof |
| CN109485910A (en) * | 2018-11-30 | 2019-03-19 | 四川大学 | Flexible high-resistance combustion property biology base aerogel material and preparation method thereof |
| CN113716548A (en) * | 2021-10-13 | 2021-11-30 | 天津晨祥丰凯新材料科技有限公司 | Preparation method of carbon aerogel and precursor thereof |
| CN116655998A (en) * | 2023-06-07 | 2023-08-29 | 西华大学 | Method for preparing melamine formaldehyde resin aerogel by normal pressure drying |
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