CN109942883A - Utilize interlayer in-situ polymerization graphene/foam of polymers batch preparation - Google Patents
Utilize interlayer in-situ polymerization graphene/foam of polymers batch preparation Download PDFInfo
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- CN109942883A CN109942883A CN201910266559.1A CN201910266559A CN109942883A CN 109942883 A CN109942883 A CN 109942883A CN 201910266559 A CN201910266559 A CN 201910266559A CN 109942883 A CN109942883 A CN 109942883A
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Abstract
It is a kind of to utilize interlayer in-situ polymerization graphene/foam of polymers batch preparation, mainly include the following steps: the preparation of (1) compound between graphite layers: oxidant and the concentrated sulfuric acid being mixed and added into graphite, solid portion is isolated after standing and is washed for several times with dilute sulfuric acid；(2) the interlayer in-situ polymerization of monomer: gained compound between graphite layers in step (1) are mixed with monomer, are reacted at moderate temperatures；(3) cleaning and drying of product: step (2) resulting product is placed in drying under 30-200 DEG C of environment, obtains graphene/foam of polymers after water and alcohol repeatedly wash.Preparation process of the present invention is simple and safely controllable, and graphene dispersion is uniform in product, has that preparation flow is short, time consumption and energy consumption is few, control is simple, the advantages such as low in cost.
Description
Technical field
The present invention relates to polymer composites technical fields, and in particular to a kind of to cause monomer with compound between graphite layers
In-situ polymerization quickly prepares graphite alkene/foam of polymers preparation method.
Background technique
The unique monoatomic layer two-dimensional structure of graphene makes it have the characteristics such as excellent electricity, optics, calorifics, mechanics.
The graphene porous foam assembled based on graphene not only remains many performance advantages of graphene itself, more because
Its porous structure and show wide application in fields such as electrochemical energy storage, pollutant absorption, gas sensing, electro-magnetic wave absorptions
Prospect.Polymer is introduced in grapheme foam, the pore structure of foam can not only be regulated and controled, be can be further realized graphene
The functional modification of foam.Therefore, graphene/foam of polymers has become a kind of novel foam material being concerned in recent years
Material.
Graphene/the foam of polymers reported at this stage is utilized on previously prepared grapheme foam frame
The modes such as in-situ polymerization or blending introduce polymer.Such methods the biggest problems are that grapheme foam frame preparation.
The process is usually to utilize chemical vapour deposition technique to grow on catalyst foam surface, or pass through the porous of redox graphene
Structure is made.The former is directed not only to high energy consumption process and yield is lower.And for the latter, in the preparation and assembling of graphene oxide
In the process it is generally necessary to use concentrated acid and strong oxidizer, there are pollution discharges.Therefore, existing graphene/foam of polymers
Preparation process not only complex steps, and there is the problems such as higher cost or pollution are discharged, which has limited graphene/polymer
The production and application of foam.
Chinese patent literature has following disclosure:
Document 1 " a kind of three-dimensional graphene foam and preparation method thereof with multilevel structure "
(CN201611232796.9): being the three-dimensional grapheme matrix on foam metal (nickel foam, foam copper or foamed aluminium) skeleton
Growth has graphene nanometer sheet on surface；The three-dimensional grapheme bubble with multilevel structure supported is derived from after removing metallic framework
Foam.
Document 2 " preparation method of graphene conductive foam " (CN201210052928.5): graphite flake addition is contained into nitre
In the concentrated sulfuric acid that acid is received, high-temperature acid potassium is added, 60-90 minutes is kept the temperature at 35~40 DEG C, water is added under magnetic agitation, adds
Graphene oxide is made in the hydrogen peroxide that concentration is 30% after separation；Finally foam dispersion is had in the water of graphene oxide, is fished out
Reduction reaction is carried out after foam out, obtains the conductive foam of the graphene coated conductive layer in surface.
Document 3 " expandable polystyrene bead and preparation method of inflatable few layer graphene "
(CN201610079099.8): electrochemical intercalation being carried out to natural flake graphite with the concentrated sulfuric acid, is lacked by ultrasonic vibration
Layer graphene, then inflatable few layer graphene and polystyrene monomers suspension polymerisation is made in its secondary intercalation, product, resistance is made
Fuel efficiency fruit is good, and foam board flame retardant rating as made from it reaches B1 grades.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies of the prior art and provide a kind of simple process, process is short, and low energy consumption, no dirt
Dye discharge utilizes interlayer in-situ polymerization graphene/foam of polymers batch preparation.
To achieve the above object, the technical solution adopted by the present invention is that: oxidant, the concentrated sulfuric acid are mixed into system with graphite first
Obtain compound between graphite layers；It is mixed with monomer then and causes interlayer home position polymerization reaction, to remove graphene, stone is made
Black alkene/foam of polymers.
Of the invention prepares graphene/foam of polymers preparation method using interlayer in-situ polymerization batch, specifically includes
Following steps:
(1) preparation of compound between graphite layers: being mixed and added into graphite for oxidant and the concentrated sulfuric acid, isolates after standing solid
Body portion is simultaneously washed for several times with dilute sulfuric acid.
(2) the interlayer in-situ polymerization of monomer: gained compound between graphite layers in step (1) are mixed with monomer, appropriate
At a temperature of reacted.
(3) cleaning and drying of product: step (2) resulting product after water, alcohol repeatedly wash, is placed in 30-200 DEG C of ring
It is dry under border, obtain graphene/foam of polymers.
Further, oxidant described in step (1) be molysite, cobalt salt, nickel salt, mantoquita, zinc salt, manganese salt, ferrate,
Permanganate, hypochlorite, persulfate, bichromate, concentrated nitric acid or their mixture.
Further, the mass volume ratio of oxidant and the concentrated sulfuric acid is 0.5-40g:100mL in step (1).
Further, graphite described in step (1) is expanded graphite, natural flake graphite, amorphous graphite, highly directional pyrolysis
Graphite, graphite electrode or flexible graphite paper.
Further, the mass volume ratio of graphite and the concentrated sulfuric acid used is 0.1-5g:100mL in step (1).
Further, monomer described in step (2) is aniline, the hydrochloric acid of pyrroles or thiophene, sulfuric acid or nitric acid solution, propylene
Amide, dopamine, methyl methacrylate aqueous solution, the melt or aqueous solution of caprolactam.
Further, the solution concentration of monomer described in step (2) is 0.002-2mol/L, or the monomer for liquid.
Further, the mass volume ratio of compound between graphite layers and monomer solution is 0.1-5g:100mL in step (2).
Present invention has an advantage that
(1) the method and process process that the present invention uses is simple, safely controllable and time consumption and energy consumption is few.It only needs at simple intercalation
Monomer polymerization can directly be caused after reason and prepare graphene/foam of polymers.Also, intercalation solution is reusable entire to guarantee
There are few pollution discharges for preparation process.
(2) method provided by the invention is applicable to the preparation of graphite alkene/foam of polymers, and batch may be implemented
Preparation, can further expansion graphene/foam of polymers such as battery capacitor, senser element, electromagnetic shielding, pollutant absorption
The extensive use in equal fields.
(3) this method has that product structure is uniform, preparation flow is short, time consumption and energy consumption is few, control is simple, low in cost etc. excellent
Gesture.Importantly, this method is applicable to the quick preparation of graphite alkene/foam of polymers and mass production, it is stone
Black alkene/foam of polymers is commercially produced and using providing effective way.
Detailed description of the invention
Fig. 1 is the digital photograph of compound between graphite layers obtained and corresponding graphene/foam of polymers in the present invention.
Fig. 2 and Fig. 3 is respectively the SEM figure of 4 sample of embodiment 2 and embodiment in the present invention.
Specific embodiment
The present invention will be further described in the following with reference to the drawings and specific embodiments.
Embodiment 1
(1) 2g iron chloride and the 100mL concentrated sulfuric acid preparation of compound between graphite layers: are mixed and added into the natural scale stone of 5g
Ink, suction filtration is isolated solid portion and is washed with the dilute sulfuric acid of 1mol/L after standing 6h.
(2) gained compound between graphite layers in step (1) the interlayer in-situ polymerization of monomer: are added 0.1mol/L pyrroles's
In sulfuric acid solution (100mL), reacted for 24 hours at 0-5 DEG C.
(3) cleaning and drying of product: suction filtration isolates solid portion, and product is placed in after water and alcohol wash 5 times in turn
It is dry in 60 DEG C of convection ovens, obtain graphene/polypyrrole porous foam.
(4) gained graphene/polypyrrole porous foam conductivity reaches 130S/cm.
Embodiment 2
(1) preparation of compound between graphite layers: 2g potassium peroxydisulfate, which is mixed and added into a tablet quality with the 100mL concentrated sulfuric acid, is
The flexible graphite paper of 3g stands and takes out graphite paper afterwards for 24 hours and rinsed with the dilute sulfuric acid of 1mol/L.
(2) the interlayer in-situ polymerization of monomer: the dopamine that gained graphite paper in step (1) is placed in 0.05mol/L is water-soluble
In liquid (100mL), 4h is reacted at room temperature.
(3) cleaning and drying of product: taking out graphite paper from the reaction solution of step (2), after water and alcohol wash in turn,
It is placed in drying in 40 DEG C of convection ovens, obtains graphene/poly-dopamine foam.
(4) gained graphene/poly-dopamine foam is to Pb2+、Cd2+And Cu2+Etc. heavy metal ion adsorptive value difference
For 163.0mg/g, 103.5mg/g and 89.6mg/g
Embodiment 3
(1) preparation of compound between graphite layers: 15g potassium ferrate is slowly mixed simultaneously with the 100mL concentrated sulfuric acid in ice bath
The highly oriented pyrolytic graphite of a piece of 2g is added, stands and takes out highly oriented pyrolytic graphite afterwards for 24 hours and rinsed with the dilute sulfuric acid of 1mol/L.
(2) gained highly oriented pyrolytic graphite in step (1) the interlayer in-situ polymerization of monomer: is placed in the polyphenyl of 0.1mol/L
In amine salt acid solution (100mL), react at room temperature for 24 hours.
(3) cleaning and drying of product: highly oriented pyrolytic graphite is taken out from the reaction solution of step (2), through water and alcohol wheel
After stream washing, it is placed in drying in 60 DEG C of convection ovens, obtains graphene/polyaniline foam.
(4) conductivity of gained graphene/polyaniline porous foam reaches 1120S/cm.
Embodiment 4
(1) preparation of compound between graphite layers: 5g potassium permanganate is slowly mixed and added with the 100mL concentrated sulfuric acid in ice bath
Enter the flexible graphite paper of a piece of 3g, stands and take out graphite paper afterwards for 24 hours and rinsed with the dilute sulfuric acid of 1mol/L.
(2) the interlayer in-situ polymerization of monomer: the acrylamide that gained graphite paper in step (1) is placed in 0.2mol/L is water-soluble
In liquid (100mL), in 90 DEG C of reaction 1h.
(3) cleaning and drying of product: graphite paper is taken out from the reaction solution of step (2), after methanol washs, is placed in 40
It is dry in DEG C convection oven, obtain graphene/polyacrylamide foam.
(4) gained graphene/polyacrylamide porous foam reaches 230.4mg/g to the adsorption capacity of methylene blue.
Embodiment 5
(1) 2g ammonium persulfate slowly the preparation of compound between graphite layers: is mixed and added into one piece of 3g with the 100mL concentrated sulfuric acid
Graphite electrode, stand for 24 hours afterwards take out graphite paper and with the dilute sulfuric acid of 1mol/L flushing.
(2) the interlayer in-situ polymerization of monomer: the acrylamide that gained graphite paper in step (1) is placed in 0.8mol/L is water-soluble
In liquid (100mL), in 90 DEG C of reaction 1h.
(3) cleaning and drying of product: graphite paper is taken out from the reaction solution of step (2), after methanol washs, is placed in 40
It is dry in DEG C convection oven, obtain graphene/polyacrylamide foam.
(4) gained graphene/polyacrylamide porous foam reaches 196.6mg/g to the adsorption capacity of methylene blue.
Above-mentioned concentrated sulfuric acid concentration is 98wt%, and dilute sulfuric acid concentration is 50wt%.
Claims (10)
1. a kind of utilize interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is characterised in that: by graphite linings
Between compound mixed with monomer, cause monomer in the polymerization reaction of graphite layers, to remove graphite, a step be made graphene/
Foam of polymers；Mainly include the following steps:
(1) preparation of compound between graphite layers: oxidant and the concentrated sulfuric acid are mixed and added into graphite, isolate solid part after standing
Divide and is washed for several times with dilute sulfuric acid；
(2) the interlayer in-situ polymerization of monomer: gained compound between graphite layers in step (1) are mixed with monomer, in proper temperature
Under reacted；
(3) cleaning and drying of product: step (2) resulting product is placed in 30-200 DEG C of environment after water and alcohol repeatedly wash
Lower drying, obtains graphene/foam of polymers.
2. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is special
Sign is: oxidant described in step (1) be molysite, cobalt salt, nickel salt, mantoquita, zinc salt, manganese salt, ferrate, permanganate,
Hypochlorite, persulfate, bichromate, concentrated nitric acid or their mixture.
3. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is special
Sign is: the mass volume ratio of oxidant and the concentrated sulfuric acid is 0.5-50g:100mL in step (1).
4. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is special
Sign is: graphite described in step (1) is expanded graphite, natural flake graphite, amorphous graphite, highly oriented pyrolytic graphite, graphite
Electrode or flexible graphite paper.
5. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is special
Sign is: the mass volume ratio of graphite and the concentrated sulfuric acid used is 0.1-5g:100mL in step (1).
6. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is special
Sign is: monomer described in step (2) is aniline, the hydrochloric acid of pyrroles or thiophene, sulfuric acid or nitric acid solution, acrylamide, DOPA
The aqueous solution of amine, methyl methacrylate, the melt or aqueous solution of caprolactam.
7. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is special
Sign is: the solution concentration of monomer described in step (2) is 0.002-2mol/L, or the monomer for liquid.
8. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is special
Sign is: the mass volume ratio of compound between graphite layers and monomer solution is 0.1-5g:100mL in step (2).
9. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation, it is special
Sign is: the step specifically:
(1) preparation of compound between graphite layers: it is 3g's that 2g potassium peroxydisulfate and the 100mL concentrated sulfuric acid, which are mixed and added into a tablet quality,
Flexible graphite paper stands and takes out graphite paper afterwards for 24 hours and rinsed with the dilute sulfuric acid of 1mol/L；
(2) gained graphite paper in step (1) the interlayer in-situ polymerization of monomer: is placed in the aqueous dopamine solution of 0.05mol/L
In (100mL), 4h is reacted at room temperature；
(3) cleaning and drying of product: taking out graphite paper from the reaction solution of step (2), after water and alcohol wash in turn, is placed in
It is dry in 40 DEG C of convection ovens, obtain graphene/poly-dopamine foam.
10. it is according to claim 1 using interlayer in-situ polymerization graphene/foam of polymers batch preparation,
It is characterized in that: the step specifically:
(1) 5g potassium permanganate slowly the preparation of compound between graphite layers: is mixed and added into one with the 100mL concentrated sulfuric acid in ice bath
The flexible graphite paper of piece 3g stands and takes out graphite paper afterwards for 24 hours and rinsed with the dilute sulfuric acid of 1mol/L；
(2) gained graphite paper in step (1) the interlayer in-situ polymerization of monomer: is placed in the acrylamide aqueous solution of 0.2mol/L
In, the volume of the aqueous solution is 100mL, in 90 DEG C of reaction 1h；
(3) cleaning and drying of product: taking out graphite paper from the reaction solution of step (2), after methanol washs, is placed in 40 DEG C of drums
It is dry in wind baking oven, obtain graphene/polyacrylamide foam.
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| CN111204743A (en) * | 2020-02-07 | 2020-05-29 | 西南交通大学 | Method for preparing twisted graphene by utilizing polymer spiral growth |
| CN114852998A (en) * | 2022-04-20 | 2022-08-05 | 西南交通大学 | Method for preparing polyaniline hybridized graphene material by electrochemical intercalation method |
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