CN106904603B - A kind of corrosion inhibiter microcapsules and preparation method thereof based on graphene roll - Google Patents
A kind of corrosion inhibiter microcapsules and preparation method thereof based on graphene roll Download PDFInfo
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- CN106904603B CN106904603B CN201710122017.8A CN201710122017A CN106904603B CN 106904603 B CN106904603 B CN 106904603B CN 201710122017 A CN201710122017 A CN 201710122017A CN 106904603 B CN106904603 B CN 106904603B
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- microcapsules
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- benzotriazole
- corrosion inhibiter
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention discloses a kind of corrosion inhibiter microcapsules based on graphene roll, the cyst material of the microcapsules are graphene, and the core material of the microcapsules is organic inhibitor.The invention also discloses the preparation methods of above-mentioned microcapsules, after the aqueous solution of organic inhibitor is blended with graphene oxide, corrosion inhibiter is coated in microcapsules while graphene is coiled under 80~200 DEG C of hydro-thermal process 8-24h, hydrothermal condition, core material coats quality height, and corrosion inhibiter slow release characteristic is good；This method cladding process is simple, easy to operate, does not need additionally to add auxiliary agent, preparation cost is cheap.
Description
Technical field
The present invention relates to technical field of graphene, more particularly, to a kind of corrosion inhibiter microcapsules based on graphene roll and its
Preparation method.
Background technique
Graphene (Graphene) is a kind of lamellar structure new material being made of single layer of carbon atom.It is by carbon atom with
sp2The hexagonal honeycomb lattice structure flat film of hybridized orbit composition, the flexible two-dimensional material of only one carbon atom thickness.
Graphene oxide is easily reunited, and it is therefore possible to make self curling of graphene and package using its flexibility, forms thin film shape
Shell.Since graphene is easy the characteristic of curling, it is possible to be used to prepare the Nano capsule of web-like to coat other objects
Matter.
Relative to common nano container or micro-nano capsule material, graphene is as new carbon, edge non-close,
Specific surface area with higher, nontoxic, biology and chemical inertness are strong, are prepared in micro-nano micelle with it and do not need to add
Add additional surfactant and various organic additives, it can drawing to avoid impurity when for supporting drug and catalyst and other material
Enter.Broad application prospect is all had in fields such as supercapacitor, energy storage material, catalysis, sensing and optical electro-chemistry.
At present for the research of graphene roll, focus mostly in theoretical calculation, the preparation of graphene roll, graphene roll cladding nothing
Machine composition granule etc., for Coated with Organic Matter to prepare the research of the micro-nano capsule with medicine-releasing performance relatively
It is few.Therefore, it is badly in need of an effective method, to prepare the micro-nano container using graphene as substrate.Currently, graphene roll
Preparation mainly using the hydrothermal technology under basic conditions.However, graphene roll meeting in drug cladding that the method obtains
A large amount of alkaline impurities are introduced, further carrying out washing treatment is needed, and the difficulty for further supporting drug is larger, it can hardly be to having
Machine drug is further coated and is supported, it is difficult to achieve the purpose that obtain micro-nano capsule.Meanwhile complicated operation step
Suddenly increased costs be will lead to, efficiency reduces, is not easy to promote and apply.
Summary of the invention
The invention solves first technical problem be to provide a kind of corrosion inhibiter microcapsules based on graphene roll, it is described
Microcapsules there is sustained release performance, may be used as coating additive, assign the good corrosion inhibition of coating.
The invention solves second technical problem be to overcome prior art defect, provide a kind of based on graphene roll
The preparation method of corrosion inhibiter microcapsules, it is this method simple process, economical and practical, it is convenient for large-scale preparation.
To solve first technical problem, the present invention adopts the following technical scheme:
A kind of corrosion inhibiter microcapsules based on graphene roll, the cyst material of the microcapsules is graphene oxide, described
The core material of microcapsules is organic inhibitor.
Preferably, the organic inhibitor is benzotriazole, sulfydryl benzotriazole, and benzimidazole, porphyrin etc. contain
The organic matter of amido.
To solve above-mentioned second technical problem, the present invention is adopted the following technical solutions:
A kind of preparation method of the corrosion inhibiter microcapsules based on graphene roll, comprising the following steps:
(1) organic inhibitor of the amount more than solubility is added in distilled water, stirs 20~30 min；
(2) a certain amount of graphene oxide is added in above-mentioned solution and stirs 30~60 min, and be ultrasonically treated 2~3 h,
Obtain mixed dispersion liquid；
(3) by above-mentioned dispersion solution in closed reaction vessel, hydro-thermal reaction is carried out；
(4) solid product is collected after reaction and it is dried, and obtains the graphite for coating above-mentioned organic inhibitor
Alkene rolls up microcapsules.
Preferably, step (1) described organic inhibitor should contain amido.
Preferably, the concentration of the organic inhibition agent solution, at room temperature close to saturation or supersaturation.
Preferably, the mass concentration of step (2) described graphene aqueous solution should be in 0~1 g/L.
Preferably, the temperature of step (3) described hydro-thermal reaction is 80~200 DEG C.
Preferably, the time of step (3) described hydro-thermal reaction is 4~24 h.
Preferably, the closed container is the stainless steel cauldron with polytetrafluoroethyllining lining.
Preferably, being dried mode is drying, vacuum drying or freeze-drying.
After the present invention is intended to coating and graphene oxide mixing, organic inhibitor-graphene oxide mixing is obtained
Dispersion liquid, then by hydro-thermal process, graphene oxide is made to generate charge attraction in the presence of amido, occur existing from crimping
As, formed graphene roll, and by most of organic inhibitor cladding wherein, formed microcapsule structure, obtain microcapsules this
Composite material with slow release characteristic.
Compared with prior art, the preparation method mild condition of graphene roll microcapsules provided by the invention coats process
Simply, easy to operate, it is low to the technical level requirement of operator, it is low in cost, there is high application value.Experimental result
Show that microcapsule structure prepared by the present invention is complete, it is high to the cladding quality of corrosion inhibiter, the slow of corrosion inhibiter can be completed in water
On The Drug Release.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure that 1 gained graphene roll of the embodiment of the present invention coats benzotriazole microcapsules；
Fig. 2 is 1 gained benzotriazole of the embodiment of the present invention, graphene, graphene roll cladding benzotriazole microcapsules
XRD comparison diagram；
Fig. 3 is the photoelectron of 1 gained benzotriazole of the embodiment of the present invention, graphene roll cladding benzotriazole microcapsules
Power spectrum (XPS) comparison diagram；
Fig. 4 is the release profiles that 1 gained graphene roll of the embodiment of the present invention coats benzotriazole microcapsules.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1:
A kind of preparation method for the graphene roll microcapsules coating benzotriazole, this method is by benzotriazole solution
Supersaturated solution dispersion is mixed with graphene oxide, keep graphene coiled by hydro-thermal reaction and benzotriazole coated it
In, specifically includes the following steps:
(1) 900 mg benzotriazole will be weighed, will be dissolved in 45 mL distilled water, 30min is stirred；
(2) 14 mg graphene oxides are weighed, are added in step (1) resulting solution, stir 1h, then 2 h of ultrasound, system
For at mixed dispersion liquid；
(3) step (2) resulting mixed dispersion liquid is transferred in the closed hydrothermal reaction kettle of 60 mL, 120 DEG C are lauched
8 h of thermal response；
(4) after hydro-thermal reaction, room temperature is naturally cooled to, gained suspension is centrifuged 5 min points in 8000 r/min
From, discard supernatant liquor, take lower sediment, after vacuum drying i.e. obtain graphene roll cladding benzotriazole microcapsules.
Fig. 1 is the microcapsules transmission electron microscope figure spectrum of cladding benzotriazole manufactured in the present embodiment, can from figure
To find out, after hydro-thermal reaction, graphene curling is coiled, and pattern is good.
Fig. 2 is the microcapsules XRD spectrum of cladding benzotriazole manufactured in the present embodiment, it can be seen from the figure that by
After hydro-thermal reaction, there is the characteristic peak of benzotriazole in sample, and the characteristic peak of graphene substantially completely disappears, and illustrates benzo
Triazole is covered by graphene, and covering amount is larger, so that the characteristic peak of graphene is unobvious.
Fig. 3 is the XPS map of cladding benzotriazole microcapsules manufactured in the present embodiment, it can be seen from the figure that hydro-thermal
There are the peaks C 1s and the peak O 1s for sample before reacting, and after hydro-thermal reaction, the peak N 1s occurs in graphene sample, it was demonstrated that anti-
Sample after answering is coated with benzotriazole.
Fig. 4 is the benzotriazole release profiles of microcapsules prepared by the present embodiment, it can be seen from the figure that microcapsules have
There is good benzotriazole release performance, absolutely proves that the present invention has prepared the micro- glue of the good graphene roll of sustained release performance
Capsule.
Embodiment 2:
A kind of preparation method for the graphene roll microcapsules coating benzotriazole, this method is by oversaturated benzo three
Nitrogen azoles solution mixes dispersion with graphene oxide, keeps graphene coiled by hydro-thermal reaction and coats benzotriazole wherein,
Specifically includes the following steps:
(1) benzotriazole for weighing 1000 mg is scattered in 45 mL distilled water, stirs 30min；
(2) 14 mg graphene oxides are weighed, are added in step (1) resulting solution, stir 1h, then 2 h of ultrasound, system
For at mixed dispersion liquid；
(3) step (2) resulting mixed dispersion liquid is transferred in the closed reaction kettle of 60 mL, hydro-thermal is anti-at 180 DEG C
Answer 10 h；
(4) after hydro-thermal reaction, water heating kettle is naturally cooled into room temperature, gained suspension is centrifuged in 8000 r/min
5 min separation, discards supernatant liquor, takes lower layer's pellet frozen dry, obtains the microcapsules of graphene roll cladding benzotriazole.
Other auxiliary agents are not added in the present invention, the substance being wrapped by is benzotriazole, is also possible to three nitrogen of sulfydryl benzo
One or more of mixtures of the organic matter containing amido such as azoles, benzimidazole, porphyrin.
By the graphene roll microcapsules after centrifuge separation, can be obtained by the methods of drying, vacuum drying, freeze-drying
Powder can also be dispersed again in other solvents, the micro-capsule dispersion liquid of favorable dispersibility is prepared by microcapsules powder.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (5)
1. a kind of preparation method of the corrosion inhibiter microcapsules based on graphene roll, it is characterised in that the wall material of the microcapsules is oxygen
Graphite alkene, the core materials of the microcapsules are benzotriazole, the preparations of the microcapsules the following steps are included:
(1) a certain amount of benzotriazole is dissolved in distilled water, stirs 20~30min；
(2) a certain amount of graphene oxide is placed in step (1) resulting solution, stirs 30~60min, be ultrasonically treated 2~3h；
(3) dispersion liquid obtained by step (2) is placed in closed container, in 80~200 DEG C of hydro-thermal process 8-24h；
(4) solid product is collected after reaction, obtains corrosion inhibiter microcapsules after vacuum or freeze-drying.
2. preparation method according to claim 1, it is characterised in that: benzotriazole solution described in step (1), in room
It is saturated solution or supersaturated solution under temperature state.
3. preparation method according to claim 1, it is characterised in that: graphene oxide described in step (2) is by tradition
Hummers method preparation.
4. preparation method according to claim 1, it is characterised in that: the concentration of graphene oxide described in step (2) is 0
~1g/L.
5. preparation method according to claim 1, it is characterised in that: closed container described in step (3) is with poly- four
The stainless steel cauldron of vinyl fluoride liner.
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| CN107674548B (en) * | 2017-11-01 | 2019-09-13 | 青岛农业大学 | A kind of preparation method based on magnetic gradient self-healing corrosion-inhibiting coating |
| CN109913075A (en) * | 2019-03-29 | 2019-06-21 | 秾源科技(北京)有限公司 | A kind of electric-heating coatings and preparation method thereof |
| CN110240156B (en) * | 2019-06-20 | 2022-07-22 | 付睿 | Graphene concentrated polycondensation adhesive and preparation method and application thereof |
| CN111926333B (en) * | 2020-08-10 | 2022-06-24 | 惠博新型材料有限公司 | Preparation method of composite corrosion inhibitor for treating hot-dip plated waste plates |
| CN114643027A (en) * | 2022-03-28 | 2022-06-21 | 国网江苏省电力有限公司电力科学研究院 | Composite graphene microcapsule and preparation method and application thereof |
| CN115058173A (en) * | 2022-07-09 | 2022-09-16 | 国网福建省电力有限公司电力科学研究院 | Graphene-based self-repairing anticorrosive coating and preparation method and application thereof |
| CN115612376B (en) * | 2022-11-12 | 2023-09-05 | 广东百川化工有限公司 | Preparation method of water-based paint |
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