CN106280578B - A kind of limbic function graphite alkene, preparation method and the purposes for being used to prepare anticorrosive paint - Google Patents
A kind of limbic function graphite alkene, preparation method and the purposes for being used to prepare anticorrosive paint Download PDFInfo
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- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention belongs to the functionalization of graphene and application field, it is related to a kind of limbic function graphite alkene, preparation method and the purposes for being used to prepare anticorrosive paint.The present invention method be using chlorate, the concentrated sulfuric acid and hydrogen peroxide system to graphene carry out functionalization, obtain carboxylic group selective modification the lamella edge of complete structure limbic function graphite alkene；Gained limbic function graphite alkene individually film forming and/or with anticorrosion paint formulation component composite membrane-forming, limbic function graphite alkene anticorrosive paint can be made.The method and process that the present invention prepares limbic function graphite alkene is simple, efficient, graphene is not only overcome to be difficult to handle, be easy the problem of accumulation, impart graphene solution machinability and handlability, simultaneously, avoid to graphene sheet layer structural damage, realize the holding of graphene sheet layer structure and characteristic, the anticorrosion ability of limbic function graphite alkene anticorrosive paint obtained is good, applied widely.
Description
Technical field
The invention belongs to the functionalization of graphene and application field, it is related to a kind of limbic function graphite alkene, its preparation side
Method and be used to prepare anticorrosive paint purposes more particularly to a kind of carboxylic group selective modification in complete graphene sheet layer
Limbic function graphite alkene, preparation method and the purposes for being used to prepare limbic function graphite alkene anticorrosive paint at edge.
Background technology
Since 2004 are found, graphene is concerned as a kind of new carbon.Grapheme material can be in height
The fields such as performance nanometer electronic device, photoelectric device, gas sensor, composite material, field emmision material and energy stores obtain wide
General application.It is stacked with problem in view of between the hardly possible dispersibility and lamella of graphene, the functional modification to graphene is even more
The commercial application potentiality of graphene is widened.Graphene oxide (GO) is the most typical limbic function graphite by extensive experimentation
Alkene, there are the functional groups such as a large amount of carboxyls, epoxy group, hydroxyl and carbonyl, these groups may make graphene oxide molten on lamella
There is preferable dispersibility in liquid.But while introducing oxygen-containing functional group, conjugated structure that graphene sheet layer itself has
It is greatly destroyed, even if can remove the oxygen-containing group on lamella to a certain extent by various restoring method, what is obtained goes back
Former graphene oxide (RGO) lamella still defect or hole (Kris Erickson, Rolf with a large amount of unrepairables
Erni,Zonghoon Lee,Nasim Alem,Will Gannett,Alex Zettl,Determination of the
Local Chemical Structure of Graphene Oxide and Reduced Graphene Oxide,
Adv.Mater.2010,22,4467-4472) so that the characteristic and graphene of graphene oxide and/or redox graphene
There is a big difference for intrinsic many excellent physicochemical characteristics.
Anticorrosion with coat is easy, economical, applicable with it, not by equipment shape constrain and have the characteristics that decorative effect and
Surfacecti proteon field is widely used.Since graphene is with unique by sp2The bi-dimensional cellular shape that the carbon atom of hydridization is constituted
Structure and excellent thermal stability and chemical stability, graphene can between the materials such as metal surface and interface and active material formation
Barrier layer is managed, the scattering and permeating of gas or fluid molecule is effectively prevented, it is potential to become a kind of excellent protective coating material.Mesh
Before, graphene have been applied to anticorrosion with coat in some terms, being broadly divided into two methods：(1) in formulation for coating material preparation process
In directly use graphene, however, used graphene is difficult to disperse so that preparation method for coating is cumbersome, time-consuming, and
Cause prepared coating homogeneity, stability poor；(2) the machinable oxidation stone of solution is used in formulation for coating material preparation process
Black alkene or derivatives thereof greatly lowers however, since graphene oxide or derivatives thereof has the hole that can not largely repair
Validity of the graphene as corrosion-inhibiting coating, and coating use scope is restricted, if any can not be applicable in Yu Haiyang ring
Border, some are not used to hot environment.
104445163 A of CN disclose a kind of preparation method of carboxylated graphene, include the following steps：1.1 prepare oxygen
Graphite alkene suspension；1.2 use reducing agent hydrazine hydrate reduction graphene oxide, prepare graphene turbid solution；1.3 by graphene
Suspension is cooled to 70~80 DEG C, and the alcoholic solution of aminophenyl acid and isoamyl nitrite is added, adjusts the content of each component, so
After highly basic is added, 24~48h of condensing reflux in 70~80 DEG C of oil baths, obtain carboxylated graphene presoma turbid solution；1.4
The presoma turbid solution of acidic graphite alkene is obtained with strong acid adjustment pH to 5~6；1.5 will be in acidic carboxypolymer graphite alkene turbid solution
Solid matter with deionized water elute filtering to pH to 6~7, obtain aqueous carboxylated graphene；1.6 freeze-dryings, obtain
Carboxylated graphene powder.But as previously mentioned, the graphene oxide layer used even across various reduction treatments, itself
Defect with a large amount of unrepairables or hole, this greatly constrains graphene and is preventing gas or fluid molecule scattering and permeating side
The application in face.
Invention content
To overcome the deficiencies of existing technologies, the present invention provides a kind of new graphite olefinic functionalities simple for process, at low cost
Change method, while solving hardly possible dispersibility, easy stackability and the structure Preserving problems of graphene in the prior art, and answered
Graphene anticorrosive paint field is used, limbic function graphite alkene anticorrosive paint has been made, it is good and suitable with anticorrosion ability
With the wide feature of range.
In order to achieve the above object, the present invention adopts the following technical scheme that：
In a first aspect, the present invention provides a kind of limbic function graphite alkene, in the limbic function graphite alkene, carboxyl
It modifies to group selectivity at the edge of the graphene sheet layer of complete structure.
The present invention limbic function graphite alkene have complete lamellar structure so that graphene sheet layer prevent gas or
The upper efficiency of liquid diffusion greatly improves, meanwhile, the edge of lamella is modified with carboxylic group, is improving graphene sheet layer dispersibility
Meanwhile being stacked with for piece interlayer is prevented, preventing gas or liquid scattering and permeating to effectively improve graphene sheet layer
On utilization rate.
Second aspect, the present invention provide the preparation method of limbic function graphite alkene as described in relation to the first aspect, the side
Method is：By graphene dispersion in the mixed solution of chlorate, the concentrated sulfuric acid and hydrogen peroxide, mixed solution is obtained, side is obtained by the reaction
Edge functionalization graphene.
Preferably, preparation method disclosed in the prior art may be used in the preparation method of graphene of the present invention, such as
Can be but be not limited to mechanical stripping method, ball-milling method, ultrasonic method, turbulene method or supercritical fluid method etc..
Preferably, the chlorate includes any one in sodium chlorate, potassium chlorate, magron or calcium chlorate or at least two
The mixture of kind, but it is not limited to the above-mentioned chlorate enumerated, other chlorates that can reach same effect are used equally for this hair
It is bright.
Preferably, the mass concentration of the concentrated sulfuric acid is 98%.
Preferably, the mass concentration of hydrogen peroxide is 30%.
Preferably, the mass ratio of the graphene and chlorate is 1:(1~10), may be, for example, 1:1、1:2、1:3、1:4、
1:4.5、1:5、1:6、1:7、1:8、1:9 or 1:10 etc., preferred mass ratio is 1:(3~6).
Preferably, in the mixed solution graphene a concentration of 0.1~50mg/mL, may be, for example, 0.1mg/mL,
0.5mg/mL、0.9mg/mL、1mg/mL、1.5mg/mL、2mg/mL、3mg/mL、5mg/mL、6.5mg/mL、8mg/mL、9mg/
mL、10mg/mL、11mg/mL、12mg/mL、13mg/mL、15mg/mL、17mg/mL、20mg/mL、23mg/mL、25mg/mL、
27.5mg/mL, 30mg/mL, 32.5mg/mL, 35mg/mL, 38mg/mL, 40mg/mL, 44mg/mL, 47mg/mL or 50mg/mL
Deng preferred a concentration of 0.9~20mg/mL.
Preferably, the volume ratio of the hydrogen peroxide and the concentrated sulfuric acid is 1:(100~1:10000) it, may be, for example, 1:100、1:
150、1:200、1:300、1:500、1:600、1:700、1:800、1:1000、1:1200、1:1500、1:1800、1:2000、1:
2350、1:2600、1:2800、1:3000、1:3200、1:3500、1:3700、1:4000、1:4200、1:4500、1:4700 or
1:5000 etc., preferred volume ratio is 1:(200~5000).
Preferably, the time of the reaction be 0.5~48 hour, may be, for example, 0.5 hour, 1 hour, 2 hours, 4 hours,
5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 13 hours, 15 hours, 17.5 hours, 20 hours, 24 hours, 26 hours,
28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 42 hours, 46 hours or 48 hours, the preferred time was 2
~10 hours；
Preferably, the temperature of the reaction be 0~90 DEG C, may be, for example, 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 35
DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C or 90 DEG C etc., preferred temperature is 0~50 DEG C.
Preferably, the method further includes after completion of the reaction, the step of detached and washed.
The third aspect, the present invention provide a kind of limbic function graphite alkene anticorrosive paint, and the anticorrosive paint contains first
Limbic function graphite alkene described in aspect.
Limbic function graphite alkene anticorrosive paint of the present invention can be limbic function graphite alkene one pack system anti-corrosion
Coating can also be limbic function graphite alkene composite anticorrosion coating.
Limbic function graphite alkene one pack system anticorrosive paint in the present invention refers to：The anticorrosive paint is by limbic function fossil
What black alkene and dispersant formed.
Limbic function graphite alkene composite anticorrosion coating in the present invention refers to：Other than limbic function graphite alkene and divide
Further include any one in film forming agent, filler, auxiliary agent or curing agent or two or more combinations except powder.
Preferably, the film forming agent is organic polymer, preferably epoxy resin, acrylate, phenolic resin, polyurethane
Or any one in alkyd resin or two or more combinations, but it is not limited to the above-mentioned film forming agent enumerated, other this fields
It prepares the common film forming agent of anticorrosive paint and can also be used for the present invention..
Preferably, it is in terms of 100% by the gross mass of anticorrosive paint, the mass percent of the film forming agent is 0~80%, and
Not comprising 0%, may be, for example, 0.01%, 0.1%, 0.2%, 0.5%, 1%, 5%, 10%, 13%, 15%, 20%, 25%,
28%, 30%, 35%, 40%, 45%, 47.5%, 50%, 55%, 57%, 60%, 70%, 75% or 80% etc..
Preferably, the filler is silica, zinc oxide, titanium dioxide, alundum (Al2O3), magnesium silicate, alumina silicate, sulphur
Any one in sour calcium, calcium carbonate or two or more combinations, but it is not limited to the above-mentioned filler enumerated, other this field systems
The standby common filler of anticorrosive paint can also be used for the present invention.
Magnesium silicate in the present invention can be commercially available magnesium silicate, can also be the mineral containing magnesium silicate, such as talcum
Powder etc.；Alumina silicate in the present invention can be commercially available alumina silicate, can also be the mineral containing alumina silicate, such as china clay and height
Ridge soil etc.；Calcium sulfate in the present invention is also known as land plaster；Calcium carbonate in the present invention can be commercially available calcium carbonate, can also
It is the mineral containing calcium carbonate, such as carclazyte.
Preferably, it is in terms of 100% by the gross mass of anticorrosive paint, the mass percent of the filler is 1~20%, such as
Can be 1%, 3%, 5%, 7%, 10%, 12.5%, 13.5%, 15%, 18% or 20% etc..
Preferably, the auxiliary agent is arbitrary in organosiloxane, surfactant, polyacrylic acid, carboxymethyl cellulose
A combination of one or more, but it is not limited to the above-mentioned auxiliary agent enumerated, other this fields prepare anticorrosive paint and commonly help
Agent can also be used for the present invention.
Preferably, it is in terms of 100% by the gross mass of anticorrosive paint, the mass percent of the auxiliary agent is 1~20%, such as
Can be 1%, 2%, 4%, 6.5%, 8.5%, 10%, 13%, 15%, 17% or 20% etc..
Preferably, the curing agent is that amine curing agent, Polyurethane curing agent, phenolic resin curing agent, acrylate are solid
Any one in agent or p-methyl benzenesulfonic acid curing agent or two or more combinations, but it is not limited to the above-mentioned solidification enumerated
Agent, other curing agent that can reach same effect can also be used for the present invention.
Preferably, it is in terms of 100% by the gross mass of anticorrosive paint, the mass percent of the curing agent is 1~20%, example
Such as can be 1%, 3%, 6%, 8%, 10%, 12%, 14%, 16%, 18% or 20%.
Preferably, it is in terms of 100% by the gross mass of anticorrosive paint, the mass percent of the limbic function graphite alkene is
0.1~70%, may be, for example, 0.1%, 0.6%, 1%, 2%, 3%, 5%, 10%, 15%, 20%, 23%, 26%, 30%,
35%, 38%, 40%, 45%, 50%, 52.5%, 55%, 60%, 65% or 70% etc..
Preferably, the dispersant is water, N-Methyl pyrrolidone, n,N-Dimethylformamide, acetone, ethyl alcohol, positive fourth
Any one in alcohol or ethyl acetate or two or more combinations.
Preferably, it is in terms of 100% by the gross mass of anticorrosive paint, the mass percent of the dispersant is 5~45%, example
Such as can be 5%, 10%, 12%, 16%, 20%, 25%, 28%, 30%, 35%, 37%, 40%, 42.5% or 45%.
The limbic function graphite alkene of the present invention may be not only suitable for above-mentioned limbic function graphite alkene one pack system anti-corrosion
Coating and limbic function graphite alkene composite anticorrosion coating, apply also for a variety of preparation formulas of other anticorrosive paints.
Fourth aspect, the present invention provides the preparation sides of the limbic function graphite alkene anticorrosive paint as described in the third aspect
Method.
Since the limbic function graphite alkene anticorrosive paint in the present invention can be specifically limbic function graphite alkene single group
Divide anticorrosive paint or limbic function graphite alkene composite anticorrosion coating, thus is had differences in preparation method.Specifically
The preparation method of ground, limbic function graphite alkene one pack system anticorrosive paint and limbic function graphite alkene composite anticorrosion coating respectively
It is as follows：
For limbic function graphite alkene one pack system anticorrosive paint, preferred preparation method is：By limbic function fossil
Black alkene is added in dispersant, and mechanical agitation 1~for 24 hours, limbic function graphite alkene anticorrosive paint is obtained, which is side
Edge functionalization graphene one pack system anticorrosive paint.
For limbic function graphite alkene composite anticorrosion coating, preferred preparation method is：By limbic function graphite
Any one or two or more combinations in alkene and film forming agent, filler, auxiliary agent or curing agent are added in dispersant, are stirred
1~for 24 hours, defoaming is stood, limbic function graphite alkene anticorrosive paint is obtained, which is that limbic function graphite alkene is compound
Anticorrosive paint.
To sum up, prepared limbic function graphite alkene can direct formation of film at surface to prepare one pack system limbic function graphite alkene anti-
Rotten coating, or the auxiliary elements composite membrane-formings such as film forming agent, filler is combined to prepare limbic function graphite alkene composite anti-corrosive coating,
In addition, adding the limbic function graphite alkene in the various anticorrosion paint formulations being currently known all in the protection model of the present invention
Within enclosing.
Compared with the prior art, the present invention has following advantage：
(1) present invention proposes a kind of new graphene functionalized method, compound using chlorate, the concentrated sulfuric acid and hydrogen peroxide
Reaction system, while keeping graphene sheet layer structural intergrity, realize carboxylic group graphene edge selectivity
Functionalization；The method of the invention it is simple for process, efficient, it is at low cost, be easy to industrialized mass production.
(2) limbic function graphite alkene of the invention is complete with lamellar structure, lamella quality is high and solution can process,
Handlability is strong, the characteristics of being not easy to stack.Hardly possible dispersibility, easy stackability and the structure for solving graphene in the prior art are kept
Difficult problem.
(3) the complete lamellar structure of limbic function graphite alkene based on the present invention and excellent physicochemical characteristic, using this
Limbic function graphite alkene anticorrosive coating prepared by the limbic function graphite alkene of invention has excellent anti-corrosion property, can
It is widely used in the surface and interface corrosion protection that land, ocean and daily life are related to, in addition, limbic function graphite alkene anticorrosion
Other physics, chemistry and the biological nature that coating does not have with some other nano materials also, such as antibacterial, taste removal, anti-ageing
Change and uvioresistant characteristic.
Description of the drawings
Fig. 1 is the transmission electron microscope photo of limbic function graphite alkene prepared by the embodiment of the present invention 1.
Fig. 2 is the Raman spectrogram that the embodiment of the present invention 1 prepares limbic function graphite alkene.
Fig. 3 is the x-ray photoelectron spectroscopy figure that the embodiment of the present invention 1 prepares limbic function graphite alkene.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
(1) graphene prepared by 300 milligrams of turbulene methods is added to 200ml H2SO4(98%), 1.8g NaClO3And 1ml
H2O2(30%) in mixed system, 8h is stirred under room temperature (25 DEG C), is then washed product repeated centrifugation, to obtain carboxyl
Group selectivity modifies the limbic function graphite alkene at lamella edge.
(2) 2.5mg limbic function graphites alkene, 300mg phenolic resin, 40mg land plasters filler, 20mg polypropylene are weighed
Acid assistant and 30mg p-methyl benzenesulfonic acid curing agent are scattered in 100ml water, and limbic function graphite alkene is obtained through 5h mechanical agitations
Composite anticorrosion coating.
It is coated to substrate surface using spraying method, after drying, obtains limbic function graphite alkene composite anti-corrosive coating.
Fig. 1 and Fig. 2 is the transmission electron microscope photo and carbon raman spectrum of limbic function graphite alkene, shows the complete of its structure
Property and high quality；
Fig. 3 is that the x-ray photoelectron spectroscopy of limbic function graphite alkene shows it essentially from lamella through being fitted carbon peak
The carboxylic group at edge；
The limbic function graphite alkene anticorrosive paint that table 1 shows the present embodiment has excellent anticorrosive property.
Embodiment 2
(1) graphene prepared by 1000 milligrams of turbulene methods is added to 200ml H2SO4(98%), 1.8g NaClO3With
0.04ml H2O2(30%) in mixed system, 4h is stirred at 15 DEG C, then washes product repeated centrifugation, to obtain carboxyl
Group selectivity modifies the limbic function graphite alkene at lamella edge.
(2) 5mg limbic function graphites alkene, 60mg epoxy resin, 8mg talcum powders, 10mg tributyl phosphates are weighed
Auxiliary agent and 5mg m-phenylene diamine (MPD) curing agent are scattered in 80ml N-Methyl pyrrolidones, and limbic function is obtained through 5h mechanical agitations
Graphene composite anticorrosion coating.
It is coated to substrate surface using spraying method, after drying, obtains limbic function graphite alkene composite anti-corrosive coating.
The limbic function graphite alkene anticorrosive paint that table 1 shows the present embodiment has excellent anticorrosive property.
Embodiment 3
(1) graphene prepared by 200 milligrams of mechanical stripping methods is added to 10ml H2SO4(98%), 2g KClO3With
0.01ml H2O2(30%) in mixed system, 10h is stirred at 0 DEG C, then washes product repeated centrifugation, to obtain carboxyl
Group selectivity modifies the limbic function graphite alkene at lamella edge.
(2) 70mg limbic function graphite alkene is weighed to be scattered in 30ml water, it is uniform through 1h mechanical agitations, obtain edge work(
It can graphite alkene one pack system anticorrosive paint.
It is coated to substrate surface in the way of brushing, after drying, obtains limbic function graphite alkene one pack system corrosion-inhibiting coating.
The limbic function graphite alkene anticorrosive paint that table 1 shows the present embodiment has excellent anticorrosive property.
Embodiment 4
(1) graphene prepared by 600 milligrams of ball-milling methods is added to 200ml H2SO4(98%), 1.8g NaClO3With
0.04ml H2O2(30%) in mixed system, 2h is stirred at 45 DEG C, then washes product repeated centrifugation, to obtain carboxyl
Group selectivity modifies the limbic function graphite alkene at lamella edge.
(2) weigh 5mg limbic function graphites alkene, 140mg Hydroxylated acrylic resins, 10mg aerosils filler,
12mg carboxymethyl celluloses auxiliary agent and 10mg diisocyanate curing agents are scattered in the mixing dispersion of 100ml n-butanols and water
In agent, limbic function graphite alkene composite anticorrosion coating is obtained through 5h mechanical agitations.
It is coated to substrate surface using spraying method, after drying, obtains limbic function graphite alkene composite anti-corrosive coating.
The limbic function graphite alkene anticorrosive paint that table 1 shows the present embodiment has excellent anticorrosive property.
Comparative example 1
Weighing 2.5mg graphene oxides, (containing the functional groups such as carboxyl, hydroxyl, carbonyl, lamellar structure has and can not largely repair
Multiple defect or hole), 300mg phenolic resin, 40mg land plasters filler, 20mg polyacrylic acid auxiliary agent, 30mg p-methyl benzenesulfonic acid it is solid
Agent obtains graphite oxide alkenyl anticorrosive paint in 100ml water, through 5h mechanical agitations.
It is coated to substrate surface using spraying method, after drying, obtains graphite oxide alkenyl corrosion-inhibiting coating.
It is coated to substrate surface in the way of brushing, after drying, obtains limbic function graphite alkene one pack system corrosion-inhibiting coating.
Comparative example 2
In addition to replacing with 2.5mg steps without step (1) and by the 2.5mg limbic function graphite alkene that step (2) uses
Suddenly outside the graphene that prepared by the turbulene method in (1), other preparation methods and condition are same as Example 1.
It is coated to substrate surface using spraying method, after drying, obtains graphene-based corrosion-inhibiting coating.
The graphene-based anticorrosive paint that this comparative example obtains is uneven, easily precipitates, and anticorrosive property is very poor.
Table 1 gives the limbic function graphite alkene corrosion-inhibiting coating of 1-4 preparations of the embodiment of the present invention, comparative example 1 using biography
The performance of graphene-based anticorrosive paint prepared by graphite oxide alkenyl anticorrosive paint and comparative example 2 prepared by system method, property
It can be tested according to GB/T 9755~2001.
Table 1
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (31)
1. a kind of limbic function graphite alkene, which is characterized in that in the limbic function graphite alkene, carboxylic group is selectively
It modifies at the edge of the graphene sheet layer of complete structure；
The limbic function graphite alkene is prepared via a method which to obtain：By graphene dispersion in chlorate, the concentrated sulfuric acid and double
In the mixed solution of oxygen water, mixed solution is obtained, limbic function graphite alkene is obtained by the reaction；
The mass ratio of the graphene and chlorate is 1:(1~10), a concentration of the 0.1 of graphene in the mixed solution~
The volume ratio of 50mg/mL, the hydrogen peroxide and the concentrated sulfuric acid is 1:(100~10000).
2. the preparation method of limbic function graphite alkene as described in claim 1, which is characterized in that the method is：By stone
Black alkene is dispersed in the mixed solution of chlorate, the concentrated sulfuric acid and hydrogen peroxide, obtains mixed solution, and limbic function fossil is obtained by the reaction
Black alkene；
The mass ratio of the graphene and chlorate is 1:(1~10), a concentration of the 0.1 of graphene in the mixed solution~
The volume ratio of 50mg/mL, the hydrogen peroxide and the concentrated sulfuric acid is 1:(100~10000).
3. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the system of the graphene
Preparation Method includes any one in mechanical stripping method, ball-milling method, ultrasonic method, turbulene method or supercritical fluid method.
4. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the chlorate includes
In sodium chlorate, potassium chlorate, magron or calcium chlorate any one or at least two mixture.
5. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the quality of the concentrated sulfuric acid is dense
Degree is 98%.
6. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the matter of the hydrogen peroxide
Measure a concentration of 30%.
7. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the graphene and chlorine
The mass ratio of hydrochlorate is 1:(3~6).
8. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that in the mixed solution
A concentration of 0.9~20mg/mL of graphene.
9. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the hydrogen peroxide and dense
The volume ratio of sulfuric acid is 1:(200~5000).
10. according to the method described in claim 2, it is characterized in that, the time of the reaction is 0.5~48 hour.
11. according to the method described in claim 10, it is characterized in that, the time of the reaction is 2~10 hours.
12. according to the method described in claim 2, it is characterized in that, the temperature of the reaction is 0~90 DEG C.
13. according to the method for claim 12, which is characterized in that the temperature of the reaction is 0~50 DEG C.
14. according to the method described in claim 2, it is characterized in that, the method further includes after completion of the reaction, detached
The step of with washing.
15. a kind of limbic function graphite alkene anticorrosive paint, which is characterized in that the anticorrosive paint contains described in claim 1
Limbic function graphite alkene.
16. anticorrosive paint according to claim 15, which is characterized in that the anticorrosive paint is by limbic function graphite alkene
And dispersant composition.
17. anticorrosive paint according to claim 15, which is characterized in that further include film forming agent in the anticorrosive paint, fill out
Material, auxiliary agent and curing agent.
18. anticorrosive paint according to claim 17, which is characterized in that the film forming agent is organic polymer.
19. anticorrosive paint according to claim 18, which is characterized in that the film forming agent be epoxy resin, acrylate,
The combination of any one or two kinds or more in phenolic resin, polyurethane or alkyd resin.
20. anticorrosive paint according to claim 17, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute
The mass percent for stating film forming agent is 0~80%, and does not include 0%.
21. anticorrosive paint according to claim 17, which is characterized in that the filler is silica, zinc oxide, dioxy
Change any one in titanium, alundum (Al2O3), magnesium silicate, alumina silicate, calcium sulfate, calcium carbonate or two or more combinations.
22. anticorrosive paint according to claim 17, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute
The mass percent for stating filler is 1~20%.
23. anticorrosive paint according to claim 17, which is characterized in that the auxiliary agent is organosiloxane, surface-active
Any one in agent, polyacrylic acid, carboxymethyl cellulose or two or more combinations.
24. anticorrosive paint according to claim 17, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute
The mass percent for stating auxiliary agent is 1~20%.
25. anticorrosive paint according to claim 17, which is characterized in that the curing agent is amine curing agent, Polyurethane
In curing agent, phenolic resin curing agent, acrylate cures agent or p-methyl benzenesulfonic acid curing agent any one or it is two or more
Combination.
26. anticorrosive paint according to claim 17, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute
The mass percent for stating curing agent is 1~20%.
27. anticorrosive paint according to claim 16, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute
The mass percent for stating limbic function graphite alkene is 0.1~70%.
28. anticorrosive paint according to claim 16, which is characterized in that the dispersant be water, N-Methyl pyrrolidone,
Any one in N,N-dimethylformamide, acetone, ethyl alcohol, n-butanol or ethyl acetate or two or more combinations.
29. anticorrosive paint according to claim 16, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute
The mass percent for stating dispersant is 5~45%.
30. the preparation method of the anticorrosive paint as described in claim 15 or 16, which is characterized in that the method includes following steps
Suddenly：Limbic function graphite alkene is added in dispersant, mechanical agitation 1~for 24 hours, it obtains limbic function graphite alkene anti-corrosion and applies
Material, the anticorrosive paint are limbic function graphite alkene one pack system anticorrosive paint.
31. the preparation method of the anticorrosive paint as described in claim 15 or 16, which is characterized in that the method includes following steps
Suddenly：By any one or the two or more combinations in limbic function graphite alkene and film forming agent, filler, auxiliary agent or curing agent
It is added in dispersant, stirring 1~for 24 hours, defoaming is stood, limbic function graphite alkene anticorrosive paint is obtained, which is
Limbic function graphite alkene composite anticorrosion coating.
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| CN107857258A (en) * | 2017-11-27 | 2018-03-30 | 盐城师范学院 | A kind of method of full carbon face oxidation adjusting function graphite alkene functional group species |
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| CN112441577A (en) * | 2019-08-30 | 2021-03-05 | 中国科学院宁波材料技术与工程研究所 | Graphene anti-corrosion and anti-fouling nano material and preparation method and application thereof |
| CN110746796B (en) * | 2019-11-11 | 2021-01-26 | 长沙天源羲王材料科技有限公司 | Modified graphene and preparation method of slurry containing modified graphene |
| CN111653399B (en) * | 2020-07-13 | 2021-08-06 | 诸暨初升新材料科技有限公司 | Method for preparing transparent conductive film from carboxyl functionalized graphene |
| CN114958177A (en) * | 2022-07-15 | 2022-08-30 | 内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司 | Economical and practical polyurethane-graphene primer-topcoat coating capable of prolonging service life under severe working conditions and preparation method thereof |
| CN115216199A (en) * | 2022-07-15 | 2022-10-21 | 内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司 | Economical and practical water-based epoxy graphene primer-topcoat coating capable of prolonging service life under severe working conditions and preparation method thereof |
| CN114958120A (en) * | 2022-07-15 | 2022-08-30 | 内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司 | Economical and practical acrylic graphene primer-topcoat coating capable of prolonging service life under severe working conditions and preparation method thereof |
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