CN109364870A - A kind of resistance to extreme condition layered phosphates foamed material and its preparation method and application - Google Patents
A kind of resistance to extreme condition layered phosphates foamed material and its preparation method and application Download PDFInfo
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- CN109364870A CN109364870A CN201811231980.0A CN201811231980A CN109364870A CN 109364870 A CN109364870 A CN 109364870A CN 201811231980 A CN201811231980 A CN 201811231980A CN 109364870 A CN109364870 A CN 109364870A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
The present embodiments relate to a kind of layered phosphates of resistance to extreme condition foamed materials and its preparation method and application.The layered phosphates of resistance to extreme condition foamed material provided in an embodiment of the present invention is prepared: layered phosphates, amino modified agent, water, graphene oxide and coagulator by the raw material for including following components；Preparation method includes the following steps: for layered phosphates to be dispersed in water, and amino modified agent, mixing is added；Graphene oxide is added, is mixed to form underflow；It is immersed in it in solution comprising coagulator underflow extrusion, molding, solidification；By product washing, the drying after solidification.The layered phosphates of resistance to extreme condition foamed material provided by the invention, with porous structure, have the excellent performances such as density is low, size shape is controllable, large amount of adsorption, adsorption rate are fast, acidproof, alkaline-resisting, salt tolerant, solvent resistant, corrosion-resistant, high temperature resistant, resistance to ablation, resistance to oxidation, fire-retardant, using flexible.
Description
Technical field
The present invention relates to a kind of layered phosphates of resistance to extreme condition foamed materials and its preparation method and application.
Background technique
Dangerous chemical leakage is typical safety accident, has the characteristics that risk is high, harm is big, association disaster is more.
On August 12nd, 2015, PORT OF TIANJIN cause danger chemicals explosion, leakage accident；Chemical industry occurs in succession for the ground such as Shandong, Jiangsu later
Factory's leakage, explosion accident.These accidents not only cause a large amount of casualties and property loss, and cause serious environment dirty
Dye and social adverse effect.
Dangerous chemical leakage object be usually taken wash away, fill, burning, decontamination, the methods of absorption are disposed.Wherein,
It the methods of washes away, fill, burn simple and easy to do, but be easy to cause secondary pollution；Decontamination method significant effect, but operate opposite
Complexity, higher cost, applicable object are limited.Absorption method is by physical absorption or the effect of chemisorption, by hazardous chemical
Be absorbed into adsorbent material, to interrupt the diffusion and reaction of hazardous chemical, have it is simple and easy to do, can control secondary pollution,
The advantages that applicable object is wide.
Adsorbent material is the key element for implementing absorption method.Adsorbent material for dangerous chemical leakage disposition not only needs
Excellent absorption property is wanted, and needs good resistance to extreme condition performance, this is because: (1) hazardous chemical generally has
Corrosivity and toxicity, therefore adsorbent material needs corrosion-resistant, solvent resistant；(2) dangerous chemical leakage is often with heat release, fire
The risks such as calamity, explosion, therefore adsorbent material needs good temperature tolerance, anti-flammability, ablation resistance.In addition, hazardous chemical is let out
Leakage object may flow into low-lying hole, gap or pipeline, therefore adsorbent material must size be suitable, using flexible, easy to operate.
The adsorbent material for having both above-mentioned advantage can effectively meet the needs of actual use.It is excellent how research obtains this performance
Different novel absorption material has reality, important meaning.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
The purpose of the present invention is to provide a kind of layered phosphates of resistance to extreme condition foamed material and preparation method thereof and answer
With.The layered phosphates of resistance to extreme condition foamed material provided by the invention has porous structure, has that density is low, size shape
Controllably, large amount of adsorption, adsorption rate be fast, acidproof, alkaline-resisting, salt tolerant, solvent resistant, corrosion-resistant, high temperature resistant, resistance to ablation, resistance to oxidation, resistance
The excellent performance such as combustion, using flexible.
Solution
Purpose to realize the present invention, the embodiment of the invention provides a kind of layered phosphates of resistance to extreme condition foamed material,
It is prepared by the raw material for including following components: layered phosphates, amino modified agent, water, graphene oxide and coagulator.
The embodiment of the invention provides a kind of preparation methods of the layered phosphates foamed material of resistance to extreme condition, including under
It states step: layered phosphates is dispersed in water, amino modified agent, mixing is added；Graphene oxide is added, is mixed to form dense
Slurry；It is immersed in it in solution comprising coagulator underflow extrusion, molding, solidification；By product washing, the drying after solidification.
The above-mentioned layered phosphates of resistance to extreme condition foamed material, preparation method in one possible implementation, stratiform
Phosphate includes the phosphate with layered crystal structure；Optionally, layered phosphates include the phosphorus with layered crystal structure
Sour zirconium, titanium phosphate, phosphoric acid hafnium, scandium phosphate, magnesium phosphate, calcium phosphate, aluminum phosphate, trbasic zinc phosphate, cobalt phosphate, nickel phosphate, ferric phosphate or
At least one of manganese phosphate；Still optionally further, layered phosphates include alpha-titanium phosphate or alpha zirconium phosphate.Alpha-titanium phosphate or α-
Basic zirconium phosphate all has layered crystal structure.
The above-mentioned layered phosphates of resistance to extreme condition foamed material, preparation method in one possible implementation, amido
Modifying agent include methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, ethylenediamine, ethanol amine, propane diamine, butanediamine, aziridine,
At least one of diisopropylamine or triethanolamine；Optionally, amino modified agent includes ethamine, ethylenediamine, propylamine or ethanol amine
At least one of.
The above-mentioned layered phosphates of resistance to extreme condition foamed material, preparation method in one possible implementation, stratiform
Phosphate, water, amino modified agent mass ratio be 10:(10-1000): (1-100)；It is optionally 10:(20-500): (1-
50)；Still optionally further it is 10:(50-200): (1-20).
The above-mentioned layered phosphates of resistance to extreme condition foamed material, preparation method in one possible implementation, aoxidize
Graphene is graphene oxide aqueous dispersion.
The above-mentioned layered phosphates of resistance to extreme condition foamed material, preparation method in one possible implementation, stratiform
The mass ratio of phosphate and graphene oxide is 100:(1-3000)；It is optionally 100:(1-2000)；Still optionally further it is
100:(200-1000).
The above-mentioned layered phosphates of resistance to extreme condition foamed material, preparation method in one possible implementation, aoxidize
In graphene aqueous dispersions, the mass fraction of graphene oxide is 0.01%-10%, is optionally 0.05%-5%, further
It is optionally 0.1%-3%.
The above-mentioned layered phosphates of resistance to extreme condition foamed material, preparation method in one possible implementation, solidify
Agent includes calcium chloride, sodium chloride, calcium nitrate, sodium nitrate, potassium nitrate, sodium sulphate, polyethyleneimine, cetyl trimethyl bromination
At least one of ammonium or diallyl dimethyl ammoniumchloride.
Above-mentioned preparation method in one possible implementation, coagulator with it is molten used in the solution comprising coagulator
The mass ratio of agent is 1:(10-1000)；It is optionally 1:(2-200)；It is still optionally further 1:(5-100).
In one possible implementation, solvent includes water or water and water-miscible organic solvent to above-mentioned preparation method
Mixed solvent.
The above-mentioned layered phosphates of resistance to extreme condition foamed material, preparation method in one possible implementation, ability
Field technique personnel can according to the present disclosure, such as: the type of coagulator and the solution usage amount comprising coagulator
Etc. factors selection coagulator dosage, as long as porous foam structure can be obtained.Such as: the underflow of 10g can both be immersed in 1L
Coagulating bath is carried out in solution comprising coagulator, and the solution for including coagulator with 100L is also allowed to carry out coagulating bath.
In one possible implementation, it includes: super that the mode mixed after amino modified agent is added to above-mentioned preparation method
At least one of sonication, strong stirring or strong shear mixing.The mesh of ultrasonic treatment, strong stirring or strong shear mixing
The poor layer for being to speed up layered phosphates and removing, and be allowed to be uniformly dispersed.
Above-mentioned preparation method in one possible implementation, after amino modified agent is added, the power of ultrasonic treatment >=
60W。
In one possible implementation, after amino modified agent is added, the time of ultrasonic treatment is above-mentioned preparation method
1min-12h；It is optionally 1min-1h；It is still optionally further 2-30min.
In one possible implementation, it includes: super that the mode mixed after graphene oxide is added to above-mentioned preparation method
At least one of sonication or strong stirring.It is sufficiently mixed, hybrid mode is unrestricted.
In one possible implementation, the time of solidification is 3min-3d to above-mentioned preparation method；It is optionally 1-12h；
It is still optionally further 2-5h.
Above-mentioned preparation method in one possible implementation, dry method include freeze-drying, forced air drying, oneself
It so dries, be dried in vacuo or at least one of supercritical drying.
In one possible implementation, the method that underflow is squeezed out includes that underflow is passed through needle to above-mentioned preparation method
Head, dropper, needle tubing, spray head or die extrusion.
The embodiment of the invention also provides the above-mentioned layered phosphates of resistance to extreme condition foamed material or above-mentioned preparation method systems
The layered phosphates of resistance to extreme condition foamed material dangerous chemical leakage disposition, water process, polymer composite or
Application in functional coating.
Beneficial effect
(1) preparation method of the layered phosphates of the resistance to extreme condition foamed material provided in the embodiment of the present invention, passes through amine
Base modifying agent assist layered phosphates removing be nanometer sheet (layered phosphates organic amine effect under, by multilayer lamination structure
Particle becomes the nanometer sheet of single layer structure or few layer structure), layered phosphates nanometer sheet self assembly shape is assisted with graphene oxide
At porous foam structure, foamed material obtained has excellent performance.
(2) layered phosphates of the resistance to extreme condition foamed material provided in the embodiment of the present invention has porous structure, has
Density is low, size shape is controllable, large amount of adsorption, adsorption rate are fast, acidproof, alkaline-resisting, salt tolerant, solvent resistant, corrosion-resistant, high temperature resistant,
The excellent performance such as resistance to ablation, resistance to oxidation, fire-retardant, using flexible meets the skill of the absorption method of dangerous chemical leakage object disposition
Art demand provides available material for Disaster Events such as hazardous chemical accidents.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 is the photo of alpha-titanium phosphate foam bead made from the embodiment of the present invention 1.
Fig. 2 is the photo of alpha zirconium phosphate foamed material made from the embodiment of the present invention 2.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Alpha-titanium phosphate used passes through hydro-thermal by the concentrated phosphoric acid that titanium tetrachloride and mass concentration are 85% in following embodiment
It reacts and (Bao, chenlu, etal., Ind.Eng.Chem.Res.2011 11109-11116) is made；Alpha zirconium phosphate is by oxychlorination
The concentrated phosphoric acid that zirconium and mass concentration are 85% be made by hydro-thermal reaction (Rui etc., China Science & Technology University's journal, 2000
112-6).Remaining various raw material is commercial product.
Embodiment 1
The alpha-titanium phosphate of 10g is dispersed in 190g water by the method for water bath sonicator, 10g ethylenediamine is added, stirring surpasses
Sound 5min obtains translucent dispersion liquid；
The graphene oxide aqueous dispersions that 20g mass fraction is 5% are added, it is sufficiently mixed by mechanical stirring and ultrasonic treatment
1h is closed, underflow is formed；
Underflow obtained is slowly squeezed out by syringe pump and syringe needle, drop is formed, instills cetyl trimethyl bromination
In ammonium aqueous dispersions (mass fraction of cetyl trimethylammonium bromide is 1%), ellipsoid product is formed, 2h is solidified；
By after solidification product water and ethanol washing for several times, freeze-drying, be made alpha-titanium phosphate foam bead；It is obtained
The photo of alpha-titanium phosphate foam bead is shown in Fig. 1.
Alpha-titanium phosphate foam bead obtained is characterized:
Alpha-titanium phosphate foam bead scorches 2h by alcolhol burner flame envelope, and whole process cannot be ignited, and bead global shape without
Significant change；
Alpha-titanium phosphate foam bead is soaked in concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid, the concentrated sulfuric acid, sodium hydroxide solution, ammonia
In the liquid such as water, ethyl alcohol, acetone, tetrahydrofuran for 24 hours, there is not apparent deformation or disintegration；
Above-mentioned chemical liquor is adsorbed with alpha-titanium phosphate foam bead, it can quick adsorption.
Embodiment 2
The alpha zirconium phosphate of 20g is dispersed in 180g water by the method for water bath sonicator, 12g ethanol amine is added, stirring surpasses
Sound 3min；
The graphene oxide aqueous dispersions that 200g mass fraction is 2% are added, it is abundant by mechanical stirring and ultrasonic treatment
2h is mixed, underflow is formed；
Underflow obtained is slowly squeezed into the polyethyleneimine aqueous dispersions (matter of polyethyleneimine by syringe pump and mouth mold
Measure score be 2%) in, the moist products of formation are cut into segment, solidify 3h；
Product after solidification is washed with water for several times, after natural drying, 1h is further dried in 120 DEG C of vacuum drying ovens,
Alpha zirconium phosphate foamed material is made；Alpha zirconium phosphate foamed material photo obtained is shown in Fig. 2.
Alpha zirconium phosphate foamed material obtained is characterized:
Alpha zirconium phosphate foamed material scorches 1h by alcolhol burner flame envelope, and whole process cannot be ignited, and bead global shape without
Significant change；
Alpha zirconium phosphate foamed material is soaked in concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid, the concentrated sulfuric acid, sodium hydroxide solution, ammonia
In the liquid such as water, ethyl alcohol, acetone, tetrahydrofuran for 24 hours, there is not apparent deformation or disintegration；
Above-mentioned chemical liquor is adsorbed with alpha zirconium phosphate foamed material, it can quick adsorption.
Embodiment 3
The alpha-titanium phosphate of 10g is dispersed in 120g water by the method for water bath sonicator, 9g propylamine, stirring, ultrasound is added
30min；
The graphene oxide aqueous dispersions that 200g mass fraction is 2% are added, it is abundant by mechanical stirring and ultrasonic treatment
2h is mixed, underflow is formed；
Underflow obtained is slowly squeezed into diallyl dimethyl ammoniumchloride dispersion liquid (poly- two by syringe pump and mouth mold
The mass fraction of allyl dimethyl ammonium chloride be 3%) in, the moist products of formation are cut into segment, solidify 4h；
Product after solidification is washed with water for several times, alpha-titanium phosphate foamed material is made in freeze-drying；
Alpha-titanium phosphate foamed material obtained is characterized:
Alpha-titanium phosphate foamed material scorches 1h by alcolhol burner flame envelope, and whole process cannot be ignited, and bead global shape without
Significant change；
Alpha-titanium phosphate foamed material is soaked in concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid, the concentrated sulfuric acid, sodium hydroxide solution, ammonia
In the liquid such as water, ethyl alcohol, acetone, tetrahydrofuran for 24 hours, there is not apparent deformation or disintegration；
Above-mentioned chemical liquor is adsorbed with alpha-titanium phosphate foamed material, it can quick adsorption.
Embodiment 4
The alpha zirconium phosphate of 30g is dispersed in 170g water by the method for water bath sonicator, 36g butylamine, stirring, ultrasound is added
2h；
The graphene oxide aqueous dispersions that 200g mass fraction is 3% are added, it is abundant by mechanical stirring and ultrasonic treatment
3h is mixed, underflow is formed；
Underflow obtained by syringe pump and mouth mold is slowly squeezed into calcium chloride dispersion liquid, and (mass concentration of calcium chloride is
5%) in, the moist products of formation is cut into segment, solidify 6h；
By after solidification product water and ethanol washing for several times, freeze-drying, be made alpha zirconium phosphate foamed material；
Alpha zirconium phosphate foamed material obtained is characterized:
Alpha zirconium phosphate foamed material scorches 1h by alcolhol burner flame envelope, and whole process cannot be ignited, and bead global shape without
Significant change；
Alpha zirconium phosphate foamed material is soaked in concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid, the concentrated sulfuric acid, sodium hydroxide solution, ammonia
In the liquid such as water, ethyl alcohol, acetone, tetrahydrofuran for 24 hours, there is not apparent deformation or disintegration；
Above-mentioned chemical liquor is adsorbed with alpha zirconium phosphate foamed material, it can quick adsorption.
Embodiment 5
The alpha-titanium phosphate of 12g is dispersed in 140g water by the method for water bath sonicator, 6g ethamine, stirring, ultrasound is added
4min obtains dispersion liquid；
The graphene oxide aqueous dispersions that 70g mass fraction is 3% are added, it is sufficiently mixed by mechanical stirring and ultrasonic treatment
2h is closed, underflow is formed；
Underflow obtained is slowly squeezed out by the spray head of syringe pump and multichannel, forms drop, instills sodium chloride dispersion
In liquid (mass fraction of sodium chloride is 10%), ellipsoid product is formed, 8h is solidified；
Product after solidification is washed with water for several times, supercritical drying, alpha-titanium phosphate foam bead is made；
Alpha-titanium phosphate foam bead obtained is characterized:
Alpha-titanium phosphate foam bead scorches 2h by alcolhol burner flame envelope, and whole process cannot be ignited, and bead global shape without
Significant change；
Alpha-titanium phosphate foam bead is soaked in concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid, the concentrated sulfuric acid, sodium hydroxide solution, ammonia
In the liquid such as water, ethyl alcohol, acetone, tetrahydrofuran for 24 hours, there is not apparent deformation or disintegration；
Above-mentioned chemical liquor is adsorbed with alpha-titanium phosphate foam bead, it can quick adsorption.
Embodiment 6
The alpha-titanium phosphate of 10g is dispersed in 100g water by the method for water bath sonicator, 6g ethanol amine is added, stirring surpasses
Sound 4min；
The graphene oxide aqueous dispersions that 120g mass fraction is 2% are added, it is abundant by mechanical stirring and ultrasonic treatment
12h is mixed, underflow is formed；
Underflow obtained is slowly squeezed out by syringe pump and needle tubing, drop is formed, instills sodium chloride dispersion liquid (sodium chloride
Mass fraction be 2%) in, formed ellipsoid product, solidify 3h；
Product after solidification is washed with water for several times, alpha-titanium phosphate foam bead is made in freeze-drying；
Alpha-titanium phosphate foam bead obtained is characterized:
Alpha-titanium phosphate foam bead scorches 2h by alcolhol burner flame envelope, and whole process cannot be ignited, and bead global shape without
Significant change；
Alpha-titanium phosphate foam bead is soaked in concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid, the concentrated sulfuric acid, sodium hydroxide solution, ammonia
In the liquid such as water, ethyl alcohol, acetone, tetrahydrofuran for 24 hours, there is not apparent deformation or disintegration；
Above-mentioned chemical liquor is adsorbed with alpha-titanium phosphate foam bead, it can quick adsorption.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of layered phosphates of resistance to extreme condition foamed material is prepared: stratiform phosphoric acid by the raw material for including following components
Salt, amino modified agent, water, graphene oxide and coagulator.
2. a kind of preparation method of the layered phosphates foamed material of resistance to extreme condition, includes the following steps: layered phosphates
It is dispersed in water, amino modified agent, mixing is added；Graphene oxide is added, is mixed to form underflow；Underflow extrusion is made into its immersion
Into the solution comprising coagulator, molding, solidification；By product washing, the drying after solidification.
3. the layered phosphates of resistance to extreme condition foamed material according to claim 1 or preparation side as claimed in claim 2
Method, it is characterised in that: layered phosphates include the phosphate with layered crystal structure；Optionally, layered phosphates include tool
There are basic zirconium phosphate, titanium phosphate, phosphoric acid hafnium, scandium phosphate, magnesium phosphate, calcium phosphate, aluminum phosphate, the trbasic zinc phosphate, phosphoric acid of layered crystal structure
At least one of cobalt, nickel phosphate, ferric phosphate or manganese phosphate；Still optionally further, layered phosphates include alpha-titanium phosphate or α-
Basic zirconium phosphate.
4. the layered phosphates of resistance to extreme condition foamed material according to claim 1 or preparation side as claimed in claim 2
Method, it is characterised in that: amino modified agent includes methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, ethylenediamine, ethanol amine, the third two
At least one of amine, butanediamine, aziridine, diisopropylamine or triethanolamine；Optionally, amino modified agent include ethamine,
At least one of ethylenediamine, propylamine or ethanol amine.
5. the layered phosphates of resistance to extreme condition foamed material according to claim 1 or preparation side as claimed in claim 2
Method, it is characterised in that: layered phosphates, water, amino modified agent mass ratio be 10:(10-1000): (1-100)；It is optionally
10:(20-500): (1-50)；Still optionally further it is 10:(50-200): (1-20)；
And/or the mass ratio of layered phosphates and graphene oxide is 100:(1-3000)；It is optionally 100:(1-2000)；
It is still optionally further 100:(200-1000).
6. the layered phosphates of resistance to extreme condition foamed material according to claim 1 or preparation side as claimed in claim 2
Method, it is characterised in that: graphene oxide is graphene oxide aqueous dispersion；Optionally, the graphene oxide water dispersion
In liquid, the mass fraction of graphene oxide is 0.01%-10%；Still optionally further, in the graphene oxide aqueous dispersions,
The mass fraction of graphene oxide is 0.05%-5%；Further optionally, in the graphene oxide aqueous dispersions, oxidation
The mass fraction of graphene is 0.1%-3%.
7. the layered phosphates of resistance to extreme condition foamed material according to claim 1 or preparation side as claimed in claim 2
Method, it is characterised in that: coagulator include calcium chloride, sodium chloride, calcium nitrate, sodium nitrate, potassium nitrate, sodium sulphate, polyethyleneimine,
At least one of cetyl trimethylammonium bromide or diallyl dimethyl ammoniumchloride.
8. preparation method according to claim 2, it is characterised in that: used in coagulator and the solution comprising coagulator
The mass ratio of solvent is 1:(10-1000)；It is optionally 1:(2-200)；It is still optionally further 1:(5-100).
9. preparation method according to claim 2, it is characterised in that: the mode mixed after amino modified agent, which is added, includes:
At least one of ultrasonic treatment, strong stirring or strong shear mixing；Optionally, power >=60W of ultrasonic treatment；Further
Optionally, the time of ultrasonic treatment is 1min-12h, and further optionally, time of ultrasonic treatment is 1min-1h, then more into
Optionally, the time of ultrasonic treatment is 2-30min to one step；
And/or it includes: at least one of ultrasonic treatment or strong stirring that the mode mixed after graphene oxide, which is added,；
And/or the time of solidification is 3min-3d；It is optionally 1-12h；It is still optionally further 2-5h；
And/or dry method include in freeze-drying, forced air drying, naturally dry, vacuum drying or supercritical drying extremely
Few one kind；
It and/or by the method that underflow squeezes out include by underflow by syringe needle, dropper, needle tubing, spray head or die extrusion.
10. the layered phosphates of resistance to extreme condition foamed material described in claim 1 or preparation method system as claimed in claim 2
The layered phosphates of resistance to extreme condition foamed material dangerous chemical leakage disposition, water process, polymer composite or
Application in functional coating.
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