CN106430172A - Magnesium hydroxide/graphene oxide composite material, preparation method and applications thereof - Google Patents
Magnesium hydroxide/graphene oxide composite material, preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses a magnesium hydroxide/graphene oxide composite material, a preparation method and applications thereof, wherein the appearance of magnesium hydroxide in the composite material is flaky, the one-dimensional size is 20-500 nm, and the flaky magnesium hydroxide is uniformly dispersed on the surface of the graphene oxide and is tightly adhered onto the surface of the graphene oxide. According to the preparation method, the hypergravity method is used, and a graphene oxide dispersion liquid, a magnesium salt solution and an alkali solution are adopted as raw materials to prepare the magnesium hydroxide/graphene oxide composite material. Compared to the material in the prior art, the material of the present invention has the following advantages that the agglomeration of the graphene oxide is effectively avoided, the particle size distribution of the magnesium hydroxide is narrow, and the particle size is uniform. The method of the present invention is quick, simple and efficient and is suitable for large scale industrial production. The material of the present invention has wide application prospects in the fields of fire retardation, water treatment, and the like.
Description
Technical field
The present invention relates to halogen-free flame-retardant nano composite and preparation method thereof.More particularly, to one kind
Magnesium hydroxide/graphene oxide composite material and preparation method and application.
Background technology
Halogen containing flame-retardant is the most flame retardant products of fire-retardant application in current plastic, rubber material, mainly
It is organic fire-retardant, and its chemical property is inert, flame retardant effect relatively good with the compatibility of plastics
Good, use cost is low, and all multiple features are all that other fire retardants are irreplaceable.But, fire occurs
When, this kind of halogen fire proofing can produce substantial amounts of smog and poisonous corrosive hydrogen halides gas, causes
Secondary hazards.Thus in recent years, halogen-free flame retardants has obtained extensive concern.Halogen resistance common at present
Combustion agent mainly has aluminium hydroxide, magnesium hydroxide, phosphorus flame retardant, expansion type flame retardant etc..But for
Competence exertion antiflaming effect when needing to add relatively large for magnesium hydroxide and aluminium hydroxide, at this moment often
Impact is produced on the performance of matrix, especially affects the mechanical property of material；The thermostability of phosphorus flame retardant
Difference, volatility be big and the poor compatibility of matrix, and has molten drop phenomenon in combustion；Intumescent
Fire retardant has the shortcomings of some such as carbon-coating compactness are poor, heat stability is poor.Thus, invention is efficiently
Fire retardant or an important problem of current flame retardant area.
A kind of new carbon simple substance with hexagonal honeycomb structure that Graphene is made up of carbon atom, its once
Come out just with the electric conductivity heat conductivity of its superelevation, the specific surface area of super large, be similar to the transparent transparency with
And its excellent gas barrier property causes extensive concern.Also just because of its unique physical chemistry
Matter, Graphene also result in the interest on fire-retardant boundary.
However, single is used using Graphene as fire retardant, taking cost into account high cost, not
It is applied to large-scale application, therefore how on the basis of not affecting flame retardant effect, reduce fire retardant
Cost becomes a great subject under discussion in face of many position material supply section scholars for the pendulum.In recent years, with material science
Continuous development, constantly have new fire proofing to emerge in large numbers.One of bright spot is exactly and Graphene phase is tied
Fire-retardant dose of the graphene-based composite closing and preparing.Material supply section scholar pass through chemical means by Graphene and
Traditional fire retardant is combined, and prepares graphene-based composite flame-proof material, the resistance of this kind of composite
Combustion performance is often better than one-component in the presence of cooperative effect.But there is presently no with regard to hydroxide
The relevant report that magnesium/graphene oxide composite material uses as BACN.
Content of the invention
It is an object of the present invention to provide a kind of magnesium hydroxide/graphene oxide composite material.Prepared
Magnesium hydroxide/graphene oxide composite material in magnesium hydroxide pattern be laminar, one-dimensional a size of
20-90 nanometer, magnesium hydroxide is uniformly dispersed in surface of graphene oxide and is closely attached to graphene oxide
Surface.
Further object is that providing a kind of preparation of magnesium hydroxide/graphene oxide composite material
Method.Using gravity Method, with graphene oxide dispersion, magnesium salt solution and aqueous slkali for raw material system
Standby magnesium hydroxide/graphene oxide composite material.
High-gravity technology is to reach the new of efficient strengthening mass transfer using the centrifugal force field that high-speed rotation produces
Technology, its quick and uniform microcosmic mixing efficiency highly shortened the mix homogeneously characteristic time, full
Uniform environment required for particulate nucleation for the foot, can improve product cut size skewness to a certain extent
And the situation that repeatability is poor, process control simultaneously.Meanwhile, it can increase substantially the conversion of reaction
Rate and selectivity, significantly reduce reactor volume, simplification of flowsheet, realize the efficient section of process
Energy.Thus it is very feasible for being applied to prepare magnesium hydroxide/graphene oxide composite material by high-gravity technology
's.
High-gravity technology is applied to the preparation of magnesium hydroxide/graphene oxide composite material by the present invention first
In, and reached good preparation effect.Compared with the prior art, involved method in the present invention is fast
Speed, simple, efficiently and be applied to large-scale industrial production.
Third object of the present invention is to provide a kind of answering of magnesium hydroxide/graphene oxide composite material
With.
For reaching above-mentioned first purpose, the present invention adopts following technical proposals：
A kind of magnesium hydroxide/graphene oxide composite material, in described composite, the pattern of magnesium hydroxide is
Flake, one-dimensional a size of 20-500 nanometer, laminar magnesium hydroxide is dispersed in graphene oxide
Surface.In this composite, magnesium hydroxide can be scattered in the surface of graphene oxide very uniformly,
And narrow particle size distribution, uniform particle diameter, it is capable of the agglomeration of effective inhibited oxidation Graphene.
For reaching above-mentioned second purpose, the present invention adopts following technical proposals：
The preparation method of magnesium hydroxide/graphene oxide composite material as claimed in claim 1, including such as
Lower step：
1) graphene oxide is prepared using Hummers method, obtain graphene oxide through redispersion is dried
Dispersion liquid；
2) prepare magnesium salt solution；
3) prepare aqueous slkali；
4) first graphene oxide dispersion is added to high gravity rotating packed bed or the reaction of bushing type microchannel
In device, it is subsequently added whole magnesium salt solutions, is eventually adding aqueous slkali, reaction obtains crude product；；
5) by step 4) in the crude product that obtains through washing, drying to obtain magnesium hydroxide/graphite oxide
Alkene composite.
In described preparation process, the addition sequence of raw material is to be initially charged graphene oxide dispersion, adds
Magnesium salt solution, is eventually adding aqueous slkali.Surface of graphene oxide can be promoted using addition sequence so
The deprotonation process of negative charge, makes graphene oxide to the greatest extent may be used in the presence of the electrostatic repulsion between lamella
Can with form of single sheet exist, for magnesium hydroxide deposition growing provide more avtive spots.
Preferably, step 1) in, the concentration of described graphene oxide dispersion is 0.05-5mg/ml.More
Preferably, the concentration of described graphene oxide dispersion is 0.25-1mg/ml.To control in this concentration range
Graphene oxide dispersion as raw material, ensure that during the course of the reaction graphene oxide with monolayer or
It is that few layer of form is present in reaction system, it is to avoid the magnesium hydroxide in the product causing because concentration is excessive
Skewness or the little phenomenon of distribution density occur；If the concentration of graphene oxide is too low simultaneously,
May lead to occur what magnesium hydroxide/graphene oxide composite material and single magnesium hydroxide coexisted in product
Phenomenon.
Preferably, step 1) in, the preparation method of described graphene oxide dispersion, comprise the following steps：
A, graphite, sodium nitrate are mixed in ice bath environment with dense strong acid, wherein graphite, sodium nitrate and
The mass ratio of dense strong acid is 1：(0.25～1.5)：(5～220)；
B, add potassium permanganate to above-mentioned mixed system, the wherein mass ratio of potassium permanganate and graphite is 1:
(6～12)；
C, above-mentioned mixed system is risen under being stirred continuously uniform temperature, insulation reaction 0.5-24h；
D, above-mentioned reaction system is cooled to room temperature, is stirred continuously a certain amount of water of lower addition, wherein water
Mass ratio with dense strong acid is (0.5～1):1；
E, be stirred continuously lower to above-mentioned mixed system in add the hydrogen peroxide of a certain amount of 30wt%, its
The quality of middle hydrogen peroxide and step 4) in the mass ratio of water be 1:6.
F, the product centrifugation to obtaining, washing, lyophilization；
G, the product being dried to obtain is distributed in solvent obtains certain density graphene oxide dispersion.
Preferably, described dense strong acid is selected from the mixed of one or more of concentrated sulphuric acid, concentrated nitric acid, strong phosphoric acid
Compound.
Preferably, the temperature in described graphene oxide dispersion preparation process is 30-70 DEG C；It is highly preferred that
Described temperature is 40-60 DEG C.
Preferably, step 2) in, described magnesium salt solution is made up of magnesium salt and solvent；Described magnesium salt is selected from down
One or more of row material：Magnesium chloride, magnesium acetate, magnesium sulfate, magnesium nitrate and basic magnesium carbonate；
Described solvent is selected from one or more of following material：Water, ethanol, methanol, ethanol, ethylene glycol,
Glycerol, butanol, n-amyl alcohol, benzene,toluene,xylene, acetone, normal hexane, hexamethylene, 1- first
Base -2-Pyrrolidone, N-METHYLFORMAMIDE, ethyl acetate, butyl acetate and oxolane.
Preferably, step 2) in, the concentration of described magnesium salt solution is 1wt%-35wt%, described magnesium salt
Quality is 0.5-600 with the mass ratio of graphene oxide:1.It is highly preferred that the concentration of described magnesium salt solution is
5wt%-25wt%.Magnesium salt in this concentration range will be controlled as raw material, surface of graphene oxide can be made
All avtive spots be fully utilized.The concentration of magnesium salt is too small, can cause the waste of avtive spot,
The magnesium hydroxide distribution density that direct result shows as surface of graphene oxide reduces；Magnesium salt concentrations are excessive,
Then the magnesium hydroxide generating can be led to cannot to be all deposited on graphene oxide because of the deficiency of avtive spot
Surface, causes the mixture that product is magnesium hydroxide/graphene oxide composite material and magnesium hydroxide.(magnesium salt
Interacted by Electrostatic Absorption with graphene oxide, the charge on GO surface, the magnesium of absorption from
Subnumber mesh is also limited)
Preferably, step 3) in, described aqueous slkali is selected from one or more of following material：Hydroxide
Sodium solution, potassium hydroxide solution and ammonia；Described sodium hydroxide solution is dissolved in water for sodium hydroxide or has
The solution that machine solvent is formed；Described potassium hydroxide solution is dissolved in water for potassium hydroxide or organic solvent is formed
Solution；Described organic solvent is selected from one or more of following material：Methanol, ethanol, ethylene glycol,
Glycerol, butanol, n-amyl alcohol, benzene,toluene,xylene, acetone, normal hexane, hexamethylene, 1- first
Base -2-Pyrrolidone, N-METHYLFORMAMIDE, ethyl acetate, butyl acetate and oxolane.
Preferably, step 3) in, the concentration of described aqueous slkali is 1wt%-40wt%；Alkali in described alkali liquor
Mass ratio with magnesium salt is 0.01-100：1；Preferably, the concentration of described aqueous slkali is 6wt%-30wt%.
Aqueous slkali in this concentration range will be controlled as raw material, ensure that magnesium salt fully reacts, it is to avoid cause
Magnesium salt is superfluous..
Preferably, described graphene oxide dispersion, magnesium salt solution and aqueous slkali are respectively placed in reservoir,
In reservoir, temperature remains 20-70 DEG C.
Preferably, step 4) in, the temperature of reaction is 20-70 DEG C, and the time of reaction is 30s-2h；Excellent
Selection of land, the reaction temperature of involved reaction is 25-55 DEG C, and the time of reaction is 30s-30min.This
The bright improvement by adopting each technological parameter during high-gravity technology, and complex reaction, can will react
Time shortens to 30s-30min, greatlys save energy consumption, provides powerful guarantee for its industrial applications.
Preferably, step 4) in, the rotating speed of described high gravity rotating packed bed is 200-2500r/min.
For reaching above-mentioned 3rd purpose, the present invention adopts following technical proposals：
Magnesium hydroxide/graphene oxide composite material as above in fire-retardant and water treatment field should
With.
The application has synthesized magnesium hydroxide/graphene oxide composite material using high-gravity technology first.With now
Technology is had to compare, the magnesium hydroxide narrow particle size distribution in the composite in the present invention, uniform particle diameter, energy
Enough the surface of graphene oxide is uniformly adhered to laminar single dispersing；Compared with prior art, originally
Magnesium hydroxide pattern in product in invention is more regular, narrow particle size distribution, graphene oxide table
It is distributed more uniform on face, there is not the obvious agglomeration between magnesium hydroxide lamella.Pass through simultaneously
Optimization to charging sequence, the species of raw material, concentration and process conditions, coordinates high-gravity technology, can
So that effectively the response time 30s-30min will be foreshortened to, greatly reduce the energy consumption of production process, be work
Industryization application provides sound assurance.The present invention, using being initially charged graphene dispersing solution, adds magnesium salt molten
Liquid, is eventually adding the technique of aqueous slkali so that the electrostatic repulsion between graphene oxide layer strengthens and abundant
Stretching, extension, provide sufficient avtive spot for the growth of magnesium hydroxide simultaneously.In addition, the application first will
Magnesium hydroxide/graphene oxide composite material is applied to flame retardant area, and achieves good effect.
Compared with the prior art, involved method in the present invention is quick, simple, efficient and is applied to big
The industrialized production of scale.In the present invention, involved material has extensively in fields such as fire-retardant, water process
Application prospect.
Beneficial effects of the present invention are as follows：
1st, the present invention prepares magnesium hydroxide/graphene oxide composite material using high-gravity technology, can be in height
Under effect microcosmic mixing, magnesium hydroxide/oxygen is prepared for raw material with graphite oxide aqueous solution, magnesium salt solution and alkali liquor
Graphite alkene composite.The shape of magnesium hydroxide in prepared magnesium hydroxide/graphene oxide composite material
Looks are laminar, one-dimensional a size of 20-500 nanometer, and magnesium hydroxide is evenly distributed in surface of graphene oxide.
2nd, the inventive method is quick, simple, efficient, repeated strong, and is applied to large-scale work
Industry metaplasia is produced.
3rd, involved magnesium hydroxide-graphene oxide composite material in the present invention can be used for fire-retardant and water
Process field.
Brief description
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates the transmission electricity of the magnesium hydroxide/graphene oxide composite material of the embodiment of the present invention 1 preparation
Mirror photo.
Specific embodiment
In order to be illustrated more clearly that the present invention, with reference to preferred embodiments and drawings, the present invention is done into one
The explanation of step.In accompanying drawing, similar part is indicated with identical reference.Those skilled in the art
It should be appreciated that following specifically described content is illustrative and be not restrictive, should not be limited with this
Protection scope of the present invention.
Embodiment 1
1) prepare 1L 0.5mg/ml graphite oxide dispersion；
2) prepare the Magnesium dichloride hexahydrate aqueous solution of 0.5L 20wt%；
3) prepare the sodium hydrate aqueous solution of 0.5L 20wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali, under conditions of rotating speed is for 1500rpm, reacts 10min at 25 DEG C
Obtain magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Fig. 1 illustrates the transmission electricity of the magnesium hydroxide/graphene oxide composite material of the embodiment of the present invention 1 preparation
Mirror photo.Can clearly find out from figure, laminar magnesium hydroxide is uniformly adhered to graphite oxide
The surface of alkene, the size of magnesium hydroxide is about 40nm and size uniform, and magnesium hydroxide is in graphene oxide
Surface soilless sticking phenomenon.
Embodiment 2
1) prepare 1L 1mg/ml graphite oxide dispersion；
2) prepare the Magnesium dichloride hexahydrate aqueous solution of 0.5L 35wt%；
3) prepare the sodium hydrate aqueous solution of 0.5L 40wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali；, under conditions of rotating speed is for 2500rpm, react 5min at 35 DEG C
Obtain magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 3
1) prepare 1L 5mg/ml graphite oxide dispersion；
2) prepare the magnesium nitrate aqueous solution of 0.5L 15wt%；
3) prepare the sodium hydrate aqueous solution of 0.5L 15wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali, under conditions of rotating speed is for 1000rpm, reacts 30min at 25 DEG C
Obtain magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 4
1) prepare 1L 0.05mg/ml graphite oxide dispersion；
2) prepare the Magnesium dichloride hexahydrate aqueous solution of 0.5L 5wt%；
3) prepare the sodium hydrate aqueous solution of 0.5L 5wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali, and reaction obtains crude product；Under conditions of rotating speed is for 1500rpm,
At 25 DEG C, reaction 30s obtains magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 5
1) prepare 1L 5mg/ml graphite oxide dispersion；
2) prepare the magnesium acetate aqueous solution of 0.5L 20wt%；
3) prepare the ammonia spirit of 2.5L 20wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali, under conditions of rotating speed is for 1500rpm, reacts 10min at 25 DEG C
Obtain magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 6
1) prepare 1L0.5mg/ml graphite oxide dispersion；
2) prepare the basic magnesium carbonate ethanol solution of 0.5L 20wt%；
3) prepare the ammonia of 5.5L 20wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali, under conditions of rotating speed is for 1500rpm, 10min at 25 DEG C
Reaction obtains magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 7
1) prepare 1L 0.5mg/ml graphite oxide dispersion；
2) prepare the Magnesium dichloride hexahydrate 1-Methyl-2-Pyrrolidone solution of 0.5L 35wt%；
3) prepare the potassium hydroxide aqueous solution of 0.5L 20wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali, under conditions of rotating speed is for 1500rpm, reacts 5min at 25 DEG C
Obtain magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 8
1) prepare 1L 0.5mg/ml graphite oxide dispersion；
2) prepare the Magnesium dichloride hexahydrate aqueous solution of 0.5L 20wt%；
3) prepare the sodium hydrate aqueous solution of 3.5L 40wt%：
4) first graphene oxide dispersion is added in bushing type micro passage reaction, is subsequently added all
Magnesium salt solution, is eventually adding aqueous slkali, under conditions of rotating speed is for 1500rpm, reacts 5 at 25 DEG C
Min obtains magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 9
1) prepare 1L 0.5mg/ml graphite oxide dispersion；
2) prepare the Magnesium dichloride hexahydrate aqueous solution of 0.5L 20wt%；
3) prepare the sodium hydrate aqueous solution of 5L 20wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali, under conditions of rotating speed is for 1500rpm, reacts 10min at 70 DEG C
Obtain magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 10
1) prepare 1L 5mg/ml graphite oxide dispersion；
2) prepare the Magnesium dichloride hexahydrate aqueous solution of 0.5L 50wt%；
3) prepare the sodium hydrate aqueous solution of 0.5L 50wt%：
4) first graphene oxide dispersion is added in high gravity rotating packed bed, is subsequently added whole magnesium
Saline solution, is eventually adding aqueous slkali, under conditions of rotating speed is for 1500rpm, reacts 10min at 25 DEG C
Obtain magnesium hydroxide-oxidized graphite composite material；
5) by 4) in the magnesium hydroxide-oxidized graphite composite material that obtains through washing, drying to obtain hydrogen
Magnesium oxide-oxidized graphite composite material.
Embodiment 11：Composite of the present invention is applied to flame retardant area
By the magnesium hydroxide/graphene oxide composite material prepared by embodiment of the present invention 1-10 and polyurethane
(PU) carry out being combined obtaining magnesium hydroxide/graphene oxide/polyurethane trielement composite material, wherein hydrogen-oxygen
The addition changing magnesium/graphene oxide composite material is 2wt%, and measures institute according to GB GB 2406-80
The oxygen index (OI) (LOI) of the trielement composite material of preparation.The oxygen index (OI) 17.3% of pure PU.
Table 1：Embodiment experimental result list
The data explanation of above-mentioned experimental result：By the parameters of regulation reaction system (such as：Rotating speed,
The concentration of reactant, the species of reactant, response time, reaction temperature, charging sequence), can adjust
The shape of magnesium hydroxide in product, granular size and its surface of graphene oxide distribution situation.With
When the product of different embodiments and PU carried out the compound fire resistance to obtained composite carry out
Research, result of study shows, only the product of (2wt%) need to be added in PU and just can show on a small quantity
Its fire retardancy of raising writing, illustrates that composite involved in the present invention has excellent flame retardant effect,
It has broad application prospects in flame retardant area.
Embodiment 12：Composite of the present invention is applied to water treatment field
Dried product 0.1g prepared by the embodiment of the present invention 1 is added to the 0.001M/L of 100ml
Aqueous solution of methylene blue in (navy blue), after magnetic agitation 2h stand, the face of navy blue aqueous solution
Color gradually becomes shallower as, and eventually becomes colourless.Through specific surface area test, the specific surface area of product reaches 400m2/g.
Illustrate that composite involved in the present invention has very big specific surface, thus there is very strong absorbability,
Can be used for processing waste water from dyestuff.
Comparative example 1
The specific embodiment of this comparative example is substantially the same manner as Example 1, and difference is this comparative example
Step 4 in using traditional stirred-tank reactor.Product in this comparative example is carried out again with PU simultaneously
Close, and fire resistance test is carried out to the composite obtaining.
Comparative example 2
The specific embodiment of this comparative example is substantially the same manner as Example 1, and difference is behaviour in this example
Make in step 4, graphite oxide dispersion, magnesium salt solution and whole alkali liquor are added to hypergravity simultaneously
Reacted in RPB.Product in this comparative example is combined with PU simultaneously, and to obtaining
Composite carry out fire resistance test.
Table 1：Comparative example experimental result list
In sum, can be drawn by the comparison of embodiment and comparative example, the present invention adopts hypergravity skill
Art, in conjunction with suitable feed way, can prepare magnesium hydroxide/graphene oxide composite material.Described
In composite, the pattern of magnesium hydroxide is flake, one-dimensional a size of 20-500 nanometer, laminar hydrogen
Magnesium oxide uniformly and is closely attached to surface of graphene oxide in surface of graphene oxide branch；Hydroxide
Magnesium is in surface of graphene oxide soilless sticking.Prepared magnesium hydroxide/graphene oxide composite material can be made
It is added to the fire resistance of the composite obtained by improving in flammable macromolecular material for fire retardant.Institute
Magnesium hydroxide/the graphene oxide composite material of preparation has larger specific surface area (400m2/ g), thus
There is preferable absorbability, can be used for water treatment field.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and
It is not the restriction to embodiments of the present invention, for those of ordinary skill in the field,
Can also make other changes in different forms on the basis of described above, here cannot be to all
Embodiment be exhaustive, every belong to the obvious change that technical scheme is extended out
Change or change the row still in protection scope of the present invention.
Claims (10)
1. a kind of magnesium hydroxide/graphene oxide composite material it is characterised in that：Hydrogen in described composite
The pattern of magnesium oxide is flake, one-dimensional a size of 20-500 nanometer, and laminar magnesium hydroxide uniformly divides
It is dispersed in the surface of graphene oxide.
2. the preparation method of magnesium hydroxide/graphene oxide composite material as claimed in claim 1, it is special
Levy and be, comprise the steps：
1) graphene oxide is prepared using Hummers method, obtain graphene oxide through redispersion is dried
Dispersion liquid；
2) prepare magnesium salt solution；
3) prepare aqueous slkali；
4) first graphene oxide dispersion is added to high gravity rotating packed bed or the reaction of bushing type microchannel
In device, it is subsequently added whole magnesium salt solutions, is eventually adding aqueous slkali, reaction obtains crude product；
5) by step 4) in the crude product that obtains through washing, drying to obtain magnesium hydroxide/graphite oxide
Alkene composite.
3. the preparation method of magnesium hydroxide/graphene oxide composite material according to claim 2, its
It is characterised by：Step 1) in, the concentration of described graphene oxide dispersion is 0.05-5mg/ml.
4. the preparation method of magnesium hydroxide/graphene oxide composite material according to claim 2, its
It is characterised by：Step 2) in, described magnesium salt solution is made up of magnesium salt and solvent；Described magnesium salt is selected from following
One or more of material：Magnesium chloride, magnesium acetate, magnesium sulfate, magnesium nitrate and basic magnesium carbonate；Institute
State solvent and be selected from one or more of following material：Water, ethanol, methanol, ethanol, ethylene glycol, third
Triol, butanol, n-amyl alcohol, benzene,toluene,xylene, acetone, normal hexane, hexamethylene, 1- methyl -2-
Ketopyrrolidine, N-METHYLFORMAMIDE, ethyl acetate, butyl acetate and oxolane.
5. the preparation method of magnesium hydroxide/graphene oxide composite material according to claim 2, its
It is characterised by：Step 2) in, the concentration of described magnesium salt solution is 1wt%-35wt%；The matter of described magnesium salt
Amount is 0.5-600 with the mass ratio of graphene oxide:1；Preferably, the concentration of described magnesium salt solution is
5wt%-25wt%.
6. the preparation method of magnesium hydroxide/graphene oxide composite material according to claim 2, its
It is characterised by：Step 3) in, described aqueous slkali is selected from one or more of following material：Sodium hydroxide
Solution, potassium hydroxide solution and ammonia；Described sodium hydroxide solution is dissolved in water or organic for sodium hydroxide
The solution that solvent is formed；Described potassium hydroxide solution is dissolved in what water or organic solvent were formed for potassium hydroxide
Solution；Described organic solvent is selected from one or more of following material：Methanol, ethanol, ethylene glycol,
Glycerol, butanol, n-amyl alcohol, benzene,toluene,xylene, acetone, normal hexane, hexamethylene, 1- first
Base -2-Pyrrolidone, N-METHYLFORMAMIDE, ethyl acetate, butyl acetate and oxolane.
7. the preparation method of magnesium hydroxide/graphene oxide composite material according to claim 2, its
It is characterised by：Step 3) in, the concentration of described aqueous slkali is 1wt%-40wt%；In described alkali liquor alkali with
The mass ratio of magnesium salt is 0.01-100：1；Preferably, the concentration of described alkali liquor is 6wt%-30wt%.
8. the preparation method of magnesium hydroxide/graphene oxide composite material according to claim 2, its
It is characterised by：Step 4) in, the temperature of reaction is 20-70 DEG C, and the time of reaction is 30s-2h；Preferably
Ground, the temperature of reaction is 25-55 DEG C, and the time of reaction is 30s-30min.
9. the preparation method of magnesium hydroxide/graphene oxide composite material according to claim 2, its
It is characterised by：Step 4) in, the rotating speed of described high gravity rotating packed bed is 200-2500r/min.
10. magnesium hydroxide/graphene oxide composite material as claimed in claim 1 is in fire-retardant and water process
Application in field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510484769.XA CN106430172B (en) | 2015-08-07 | 2015-08-07 | A kind of magnesium hydroxide/graphene oxide composite material and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510484769.XA CN106430172B (en) | 2015-08-07 | 2015-08-07 | A kind of magnesium hydroxide/graphene oxide composite material and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106430172A true CN106430172A (en) | 2017-02-22 |
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Cited By (8)
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| CN107349900A (en) * | 2017-07-28 | 2017-11-17 | 广东大能新材科技有限公司 | A kind of heavy metal absorbent and its preparation |
| CN108752634A (en) * | 2018-04-10 | 2018-11-06 | 宁波工程学院 | A kind of preparation method of graphene coated hydroxide nanoparticle composite material |
| CN109233869A (en) * | 2018-08-09 | 2019-01-18 | 苏州市泽镁新材料科技有限公司 | A kind of preparation method of the high fire-retardance high thermal conductivity composite particles based on magnesium hydroxide |
| CN109503888A (en) * | 2018-11-28 | 2019-03-22 | 沈阳理工大学 | A kind of preparation method of boehmite/graphene composite material |
| CN110804245A (en) * | 2019-11-18 | 2020-02-18 | 中国科学院青海盐湖研究所 | Flame-retardant composite material and preparation method thereof |
| CN112646210A (en) * | 2019-10-11 | 2021-04-13 | 北京化工大学 | Collagen fiber-based electromagnetic shielding material with leather scraps as raw materials and preparation method thereof |
| CN113121915A (en) * | 2021-04-21 | 2021-07-16 | 广东宇豪新材料科技有限公司 | Halogen-free flame-retardant graphene modified flame-retardant polypropylene material for household appliances |
| CN113150446A (en) * | 2021-05-19 | 2021-07-23 | 广东宇豪新材料科技有限公司 | Polypropylene material |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107349900A (en) * | 2017-07-28 | 2017-11-17 | 广东大能新材科技有限公司 | A kind of heavy metal absorbent and its preparation |
| CN107349900B (en) * | 2017-07-28 | 2018-07-31 | 广东大能新材科技有限公司 | A kind of heavy metal absorbent and its preparation |
| CN108752634A (en) * | 2018-04-10 | 2018-11-06 | 宁波工程学院 | A kind of preparation method of graphene coated hydroxide nanoparticle composite material |
| CN109233869A (en) * | 2018-08-09 | 2019-01-18 | 苏州市泽镁新材料科技有限公司 | A kind of preparation method of the high fire-retardance high thermal conductivity composite particles based on magnesium hydroxide |
| CN109503888B (en) * | 2018-11-28 | 2020-09-08 | 沈阳理工大学 | Preparation method of boehmite/graphene composite material |
| CN109503888A (en) * | 2018-11-28 | 2019-03-22 | 沈阳理工大学 | A kind of preparation method of boehmite/graphene composite material |
| CN112646210A (en) * | 2019-10-11 | 2021-04-13 | 北京化工大学 | Collagen fiber-based electromagnetic shielding material with leather scraps as raw materials and preparation method thereof |
| CN112646210B (en) * | 2019-10-11 | 2022-07-05 | 北京化工大学 | Collagen fiber-based electromagnetic shielding material with leather scraps as raw materials and preparation method thereof |
| CN110804245A (en) * | 2019-11-18 | 2020-02-18 | 中国科学院青海盐湖研究所 | Flame-retardant composite material and preparation method thereof |
| CN113121915A (en) * | 2021-04-21 | 2021-07-16 | 广东宇豪新材料科技有限公司 | Halogen-free flame-retardant graphene modified flame-retardant polypropylene material for household appliances |
| CN113121915B (en) * | 2021-04-21 | 2022-03-04 | 广东宇豪新材料科技有限公司 | Halogen-free flame-retardant graphene modified flame-retardant polypropylene material for household appliances |
| CN113150446A (en) * | 2021-05-19 | 2021-07-23 | 广东宇豪新材料科技有限公司 | Polypropylene material |
| CN113150446B (en) * | 2021-05-19 | 2022-03-04 | 广东宇豪新材料科技有限公司 | Polypropylene material |
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