CN109575755A - A kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating and the preparation method and application thereof - Google Patents
A kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating and the preparation method and application thereof Download PDFInfo
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- 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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- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to the preparation technical fields of anti-corrosive metal coating, and in particular to a kind of quaternary ammoniated lignin/graphene/carbon nano-tube base composite anti-corrosive coating and the preparation method and application thereof.This method prepares quaternary ammoniated lignin graphene/carbon nano-tube dispersion liquid using ultrasound removing dispersion, then mixes with aqueous epoxy resins and waterborne curing agent, quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite water soluble corrosion-inhibiting coating is prepared.This method uses reproducible biological material lignin, it is acted on using the quaternary ammoniated, amphipathic of lignin and its π-π between graphene, hydrophobic graphene and carbon nanotube can be uniformly dispersed in aqueous epoxy resins, graphene in thus obtained coating can obstruct the intrusion of corrosion small molecule layer by layer, delay the corrosion rate of substrate.Meanwhile the addition of carbon nanotube can be played with graphene and cooperate with corrosion-resisting function, which is used for the anti-corrosion of metal and building material surface, show preferable capacitive reactance arc.
Description
Technical field
The invention belongs to the preparation technical fields of anti-corrosive metal coating, and in particular to and a kind of quaternary ammoniated lignin/graphene/
Carbon nanotube base composite anti-corrosive coating and the preparation method and application thereof.
Background technique
With becoming increasingly conspicuous for energy and environmental problem, people substitute fossil energy material using reproducible biological material
Material becomes a kind of trend.Lignin is only second to cellulose as a kind of reproducible biological material, content.Lignin conduct
A kind of by-product of papermaking wastewater is usually ignored by people, becomes the research heat of people using lignin preparation high added value material
Point.
In these years, as corrosion caused by personnel and property loss it is increasing, graphene due to its unique two
Tie up structure, make it have good barrier property, the carbon nanotube carbon nanomaterial one-dimensional as one kind, with grapheme material into
Row is compound to play synergistic effect.The barrier property and resistance to chemical corrosion of composite material can be effectively improved.
However, due to being easily clumped together with high-specific surface area and strong Van der Waals force, graphene film and carbon nanotube,
Further, since these carbon nanomaterials have hydrophobicity, be more difficult to disperse in water-based material, these reasons all limit its
Application in water-base resin composite material.
Summary of the invention
It is in order to overcome the shortcomings of the prior art and insufficient, the primary purpose of the present invention is that providing a kind of quaternary ammoniated lignin point
Dissipate the preparation method of graphene/carbon nano-tube base composite anti-corrosive coating.This method carries out quaternary ammoniated modification to lignin first, so
It is mixed afterwards with graphene and carbon nanotube, ultrasound removing dispersed graphite alkene and carbon nanotube, the quaternary amine being saturated in water phase
Change the graphene/carbon nano-tube dispersion liquid of lignin dispersion, then mixed with aqueous epoxy resins and waterborne curing agent, is prepared
The quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating.
Another object of the present invention is to provide the quaternary ammoniated lignin dispersed graphite alkene/carbon obtained by above-mentioned preparation method
Nanotube base composite anti-corrosive coating.The corrosion-inhibiting coating is at low cost, environmental-friendly, has preferable water resistance, thermal stability.
A further object of the present invention is to provide above-mentioned quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosives
The application of coating.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating, including it is following
Step:
(1) preparation of quaternary ammoniated lignin:
By lignin dissolution in sodium hydroxide solution, ultrasonic disperse obtains lignin dispersion liquid, then quaternary amine is added dropwise
Salting liquid reacts under the conditions of heating and stirring, is cooled to room temperature, obtains reaction solution, dry by reaction solution dialysis purification
Later, quaternary ammoniated lignin is obtained；
(2) preparation of quaternary ammoniated lignin dispersed graphite alkene/carbon nano tube dispersion liquid:
By quaternary ammoniated lignin dissolution Yu Shuizhong, quaternary ammoniated lignin dispersion liquid is obtained, graphene and carbon nanometer is added
Pipe, ultrasound removing, is dispersed with stirring, and is centrifuged, the graphene/carbon nano-tube dispersion liquid for the quaternary ammoniated lignin dispersion being saturated；
(3) preparation of composite anti-corrosive coating:
Graphene/carbon nano-tube dispersion liquid, the waterborne curing agent, water-base epoxy tree that the quaternary ammoniated lignin of saturation is dispersed
Rouge is uniformly mixed, and obtains coating Tooth preparation, deaeration, the surface coated in base material, solidification, is obtained described quaternary ammoniated wooden
Plain dispersed graphite alkene/carbon nanotube base composite water soluble corrosion-inhibiting coating.
Preferably, lignin described in step (1) is sodium lignin sulfonate, alkali lignin or high-boiling alcohol lignin.
Preferably, the concentration of sodium hydroxide solution described in step (1) is 20wt.%.
Preferably, the concentration of lignin dispersion liquid described in step (1) is 0.16~0.3g/mL.
Preferably, quaternary amine salting liquid described in step (1) is 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution, quality
Concentration is 60%.
Preferably, the mass ratio of the lignin in reaction solution described in step (1) and quaternary amine is 1:0.83.
Preferably, the temperature of heating described in step (1) is 85~100 DEG C.
Preferably, when a length of 4~6h of reaction described in step (1).
Preferably, room temperature described in step (1) is 20~40 DEG C.
Preferably, dialysis described in step (1) uses molecular weight to carry out for 800~1000 bag filter.
Preferably, drying described in step (1) is carried out using freeze drier, drying time 48h.
It is dark brown powder by the quaternary ammoniated lignin that step (1) obtains, after quaternary ammoniated, in lignin macromolecular
Face is successfully introduced into quaternary amine salt ion, and the charge density of lignin increases, can more effective dispersed graphite alkene and carbon nanotube.
Preferably, the concentration of quaternary ammoniated lignin dispersion liquid described in step (2) is 5~15mg/mL.
Preferably, graphene described in step (2) is the graphene of physical method removing, chemical method redox graphene
Or vapour deposition process graphene.
Preferably, carbon nanotube described in step (2) is multi-arm carbon nano-tube, single armed carbon nanotube or hydroxylating multi-arm
Carbon nanotube.
Preferably, the gross mass of addition graphene and carbon nanotube described in step (2) is the dispersion of quaternary ammoniated lignin
1/2~1 times of liquid quality.
Preferably, the quality of addition graphene and carbon nanotube described in step (2) is graphene: carbon nanotube=1:
1~1:4.
Preferably, the method for ultrasound described in step (1) and step (2) is to use under the conditions of 10~30 DEG C and 20kHz
The ice-bath ultrasonic of 100% amplitude.
It is furthermore preferred that when a length of 4~6h of ultrasound described in step (2).
Preferably, the revolving speed of stirring described in step (2) is 100rpm.
Preferably, the method for centrifugation described in step (2) is to be centrifuged 90min with 1000rpm.
The purpose of the centrifugation is to remove graphene and carbon nanotube aggregated particle unstable in mixed liquor.
Preferably, aqueous epoxy resins described in step (3) are the epoxy resin that pre-emulsified epoxide number is 51.
Preferably, waterborne curing agent described in step (3) is amine curing agent.
Preferably, the graphene/carbon of the quaternary ammoniated lignin dispersion of the saturation in coating Tooth preparation described in step (3)
The mass ratio of nanotube dispersion liquid and aqueous epoxy resins is 1:5~3:5；
Preferably, the mass ratio of the aqueous epoxy resins in coating Tooth preparation described in step (3) and waterborne curing agent
For 1:0.8~1:0.9.
Preferably, sequence mixed described in step (3) is first to disperse waterborne curing agent and quaternary ammoniated lignin
The mixing of graphene/carbon nano-tube dispersion liquid, adds aqueous epoxy resins.
Preferably, method uniformly mixed described in step (3) be at 20KHz, 15~25 DEG C ultrasonic disperse 5~
15min。
Preferably, the method for deaeration described in step (3) is to be dried in vacuo under condition of ice bath, and vacuum extracts gas
Bubble.
Preferably, base material described in step (3) is glass plate, aluminium flake or Q235 carbon steel.
Preferably, cured condition described in step (3) is to solidify 4~8h at room temperature.
Preferably, lignin described in step (3)/graphene-based composite anti-corrosive coating is with a thickness of 20~45 μm.
The present invention further provides a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating, by
Above-mentioned preparation method obtains, ZF=0.01HZUp to (0.96~2.43) × 107Ω/cm。
The present invention further provides answering for above-mentioned quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating
With the quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating is used for metal base or building materials table
The anticorrosion in face.
Compared with prior art, the present invention having the following advantages and benefits:
(1) the characteristics of containing a large amount of phenolic hydroxyl group and alcoholic extract hydroxyl group present invention utilizes quaternary ammoniated lignin, it is amphipathic with
And π-π the effect between lignin and graphene or carbon nanotube, so that quaternary ammoniated lignin becomes graphene or carbon nanotube
Dispersing agent in water phase, being dispersed in hydrophobic graphene uniform in aqueous epoxy resins, the quaternary ammoniated lignin of gained
The carbon nano tube/graphene dispersion liquid of dispersion is not required to be concentrated, and can be used to the preparation of coating.
(2) quaternary ammoniated lignin dispersing Nano carbon tubes/graphene-based composite anti-corrosive coating preparation process letter in the present invention
It is single, strong operability.Since the lignin utilized is reproducible biological material, environmentally protective, cost is relatively low, uses
It is convenient.The graphene of high degree of dispersion can obstruct the intrusion of corrosion small molecule layer by layer in coating, greatly reduce the corrosion road of small molecule
Diameter delays the corrosion rate of substrate.The coating can be widely applied to exposed metal base and other building material surfaces, and extension is protected
Protect the service life of matrix.It shows preferable capacitive reactance arc, Z in electrochemical AC impedance (EIS)F=0.01HZUp to (0.96~
2.43)×107Ω/cm。
Detailed description of the invention
Fig. 1 is transversal for the quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating prepared in embodiment 1
The SEM microscopic appearance figure in face (a) and surface (b).
Fig. 2 is compound anti-for the quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base prepared in embodiment 1 and embodiment 3
The optical microscope (amplification factor 10 × 20) of rotten coating, wherein figure (a) corresponding embodiment 1, schemes (b) corresponding embodiment 3.
Fig. 3 be in embodiment 1 quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating for preparing not
With AC impedance (EIS) figure under the time.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.For not specifically specified technological parameter, routine techniques progress can refer to.
Waterborne curing agent used in the following example is a kind of environmentally protective amine of non-volatility organic compound
Curing agent, trade mark DY-175.
Aqueous epoxy resins used in the following example are a kind of epoxy resin that the epoxide number that pre-emulsification has been got well is 51,
The trade mark is DY-128-50, E51.
Embodiment 1
The present embodiment provides a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating preparation sides
Method.
(1) sodium hydrate solid is added in 45ml deionized water, obtains using purification drying is preceding carried out by alkali lignin
The sodium hydroxide solution of 20wt.%, adds alkali lignin, and it is wooden to obtain the alkali that the sodium hydroxide that concentration is 0.16g/mL dissolves
Plain solution, ultrasonic disperse 15min.According to quality than alkali lignin: 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution=1:0.83
Proportion, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution (60wt.%) is added dropwise in above-mentioned lignin aqueous slkali,
It is stirred to react 4h at 85 DEG C, after completion of the reaction, is cooled to room temperature, obtains reaction solution, by 1000 molecular weight of reaction solution
Bag filter dialysis purification, reaction solution after the dialysis dry 48h of freeze drier obtains the quaternary ammoniated lignin of dark brown；
(2) by quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 10mg/ml is obtained,
The hydroxylating multi-arm carbon nano-tube of graphene and 3 mass parts that the physical method of 2 mass parts is removed is added to the season of 10 mass parts
Aminated lignin disperses in aqueous solution, supersonic wave cleaning machine ice-bath ultrasonic 6h at 20KHz to be utilized at 15 DEG C, is dispersed with stirring
4h, 1000rpm are centrifuged 90min, obtain the graphene of quaternary ammoniated lignin stable dispersion and the dispersion liquid of carbon nanotube, dispersion liquid
Solubility is 5mg/ml.
(3) water of the graphene/carbon nano-tube dispersion liquid and 4.25 mass parts that disperse the quaternary ammoniated lignin of 1 mass parts
After property curing agent DY-175 is mixed evenly, the aqueous epoxy resins DY-128-50 of 5 mass parts is added, E51, in room temperature
Lower mechanical stirring is uniformly mixed, the ultrasonic disperse 10min under 20KHz in supersonic cleaning machine, under vacuum drying oven condition of ice bath, very
Empty pump bubble removing；After bubble eliminates, the coating of 25 μ m-thicks is painted on Q235 carbon steel using spin coating instrument.Solidify under room temperature
5h obtains the graphene/carbon nano-tube base composite anti-corrosive coating of the quaternary ammoniated lignin dispersion.
It is microcosmic to above-mentioned lignin/graphene-based composite anti-corrosive coating progress that scanning electron microscope and optical microscopy is respectively adopted
Morphology analysis, as a result as depicted in figs. 1 and 2, it is seen that graphene and carbon nanotube are uniformly dispersed in matrix epoxy resin, are said
It is bright in aqueous epoxy resins, quaternary ammoniated lignin has preferable dispersibility to graphene and carbon nanotube.
Embodiment 2
The present embodiment provides the graphene/carbon nano-tube base composite anti-corrosives of quaternary ammoniated lignin dispersion prepared by embodiment 1
The application of coating and its reference examples.
(1) preparation of water-base epoxy coating (WEP):
By the waterborne curing agent DY-175 of 4.25 mass parts, the water-base epoxy tree of the deionized water of 1 mass parts and 5 mass parts
Mechanical stirring is uniformly mixed rouge DY-128-50 at room temperature, the ultrasonic disperse 10min under 20KHz in supersonic cleaning machine, in vacuum
Under baking oven condition of ice bath, vacuum extracts bubble；After bubble eliminates, the painting of 25 μ m-thicks is painted on Q235 carbon steel using spin coating instrument
Layer.Solidify 5h under room temperature, obtains water-base epoxy coating.
(2) preparation of the graphene-based composite anti-corrosive coating of quaternary ammoniated lignin dispersion:
By quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 10mg/ml is obtained, by 5
The graphene of the physical method removing of mass parts is added to the quaternary ammoniated lignin dispersion of 10 mass parts in aqueous solution, at 15 DEG C
Using supersonic wave cleaning machine at 20KHz ice-bath ultrasonic 6h, be dispersed with stirring 4h, 1000rpm is centrifuged 90min, obtains quaternary ammoniated wood
The graphene dispersing solution of quality stable dispersion, dispersion liquid solubility are 5mg/ml
The graphene dispersing solution of the quaternary ammoniated lignin dispersion of 1 mass parts, the waterborne curing agent DY- with 4.25 mass parts
175, the water-base epoxy DY-128-50E51 of 5 mass parts, mechanical stirring is uniformly mixed at room temperature, in supersonic cleaning machine
Ultrasonic disperse 10min under 20KHz, under vacuum drying oven condition of ice bath, vacuum extracts bubble；After bubble eliminates, spin coating is utilized
Instrument paints the coating of 25 μ m-thicks on Q235 carbon steel.Solidify 5h under room temperature, obtains the quaternary ammoniated lignin dispersion
Graphene-based composite anti-corrosive coating.
(3) preparation of the carbon nanotube base composite anti-corrosive coating of quaternary ammoniated lignin dispersion:
Preparation method is same as above, the difference is that the graphene that the physical method of 5 mass parts is removed is replaced with 5 mass parts
Hydroxylating multi-arm carbon nano-tube.
Study the electrochemical anti-corrosive performance of coating at room temperature with model CHI660 electrochemical workstation.Wherein, it has
The saturated calomel electrode of Luggin capillary is reference electrode, and platinum plate electrode is to be prepared to electrode with embodiment 1 quaternary ammoniated wooden
The graphene/carbon nano-tube base composite anti-corrosive coating of element dispersion, water-base epoxy coating manufactured in the present embodiment, uncoated Q235
Carbon steel, the graphene-based composite anti-corrosive coating of quaternary ammoniated lignin dispersion, the carbon nanotube base of quaternary ammoniated lignin dispersion are compound
Corrosion-inhibiting coating is immersed in 3h in the simulated seawater of 3.5wt%NaCl respectively as working electrode, stablizes open circuit potential (OCP)
Afterwards, with sine wave disturbance amplitude 30mV at OCP, frequency is that 100000Hz~0.01Hz progress electrochemical impedance spectroscopy (EIS) is swept
It retouches.
As a result as shown in Figure 3, it is known that the graphene/carbon nano-tube base composite anti-corrosive coating of quaternary ammoniated lignin dispersion is low
Frequency and high frequency have higher impedance arc, and water-base epoxy coating and uncoated Q235 carbon steel are only lesser out in low frequency behavior
Impedance arc, when low frequency, uncoated Q235 carbon steel ZF=0.01HZ=2.93 × 103Ω/cm, water-base epoxy coating
ZF=0.01HZ=0.84 × 104Ω/cm, the Z of the graphene-based composite anti-corrosive coating of quaternary ammoniated lignin dispersionF=0.01HZ=8.65
×106Ω/cm, the carbon nanotube base composite anti-corrosive coating Z of quaternary ammoniated lignin dispersionF=0.01HZ=1.65 × 106Ω/cm, and
The graphene/carbon nano-tube base composite anti-corrosive coating of quaternary ammoniated lignin dispersion is ZF=0.01HZ=2.43 × 107Ω/cm.Due to
Low-limit frequency (ZF=0.01Hz) at impedance modulus can be used as the semiquantitative index of coating barrier property, therefore illustrate embodiment 1 make
Standby lignin/graphene/carbon nano-tube base composite anti-corrosive coating has best Corrosion Protection.This be attributed to graphene and
The collaboration blocking effect of carbon nanotube.
Embodiment 3
The present embodiment provides a kind of preparations of the graphene/carbon nano-tube base composite anti-corrosive coating of quaternary ammoniated lignin dispersion
Method.
(1) sodium hydrate solid is added in 45ml deionized water, obtains using purification drying is preceding carried out by high-boiling alcohol lignin
To the sodium hydroxide solution of 20wt.%, high-boiling alcohol lignin is added, obtains what the sodium hydroxide that concentration is 0.16g/mL dissolved
High-boiling alcohol lignin solution, ultrasonic disperse 15min.According to quality than high-boiling alcohol lignin: the chloro- 2- Hydroxyproyl Trimethyl chlorination of 3-
3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution (60wt.%) is added dropwise to above-mentioned wood by ammonium salt solution=1:0.83 proportion
In quality aqueous slkali, it is stirred to react 4h at 85 DEG C, after completion of the reaction, is cooled to room temperature, obtains reaction solution, by reaction solution
With the bag filter dialysis purification of 800 molecular weight, the reaction solution after dialysis dries 48h with freeze drier, obtains dark brown quaternary amine
The lignin of change；
(2) by quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 10mg/ml is obtained,
The hydroxylating multi-arm carbon nano-tube of graphene and 3 mass parts that the physical method of 2 mass parts is removed is added to the season of 10 mass parts
Aminated lignin disperses in aqueous solution, supersonic wave cleaning machine ice-bath ultrasonic 6h at 20KHz to be utilized at 15 DEG C, is dispersed with stirring
4h, 1000rpm are centrifuged 90min, obtain the graphene of quaternary ammoniated lignin stable dispersion and the dispersion liquid of carbon nanotube, dispersion liquid
Solubility is 5mg/ml.
(3) water of the graphene/carbon nano-tube dispersion liquid and 4.25 mass parts that disperse the quaternary ammoniated lignin of 3 mass parts
After property curing agent DY-175 is mixed evenly, the aqueous epoxy resins DY-128-50 of 5 mass parts is added, E51, in room temperature
Lower mechanical stirring is uniformly mixed, the ultrasonic disperse 10min under 20KHz in supersonic cleaning machine, under vacuum drying oven condition of ice bath, very
Empty pump bubble removing；After bubble eliminates, the coating of 25 μ m-thicks is painted on Q235 carbon steel using spin coating instrument.Solidify under room temperature
5h obtains the graphene/carbon nano-tube base composite anti-corrosive coating of the quaternary ammoniated lignin dispersion.
Lignin manufactured in the present embodiment/graphene-based composite anti-corrosive coating ZF=0.01HZ=1.62 × 107Ω/cm；Inspection
Survey method is the same as embodiment 2.
Embodiment 4
The present embodiment provides a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating preparation sides
Method.
(1) sodium hydrate solid is added in 45ml deionized water, obtains using purification drying is preceding carried out by alkali lignin
The sodium hydroxide solution of 20wt.%, adds alkali lignin, and it is wooden to obtain the alkali that the sodium hydroxide that concentration is 0.16g/mL dissolves
Plain solution, ultrasonic disperse 15min.According to quality than alkali lignin: 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution=1:0.83
Proportion, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution (60wt.%) is added dropwise in above-mentioned lignin aqueous slkali,
It is stirred to react 6h at 85 DEG C, after completion of the reaction, is cooled to room temperature, obtains reaction solution, by 1000 molecular weight of reaction solution
Bag filter dialysis purification, reaction solution after the dialysis dry 48h of freeze drier obtains the quaternary ammoniated lignin of dark brown；
(2) by quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 5mg/ml is obtained, it will
The chemical deposition graphene of 1 mass parts and the hydroxylating multi-arm carbon nano-tube of 4 mass parts are added to the quaternary ammoniated of 10 mass parts
Lignin disperses in aqueous solution, supersonic wave cleaning machine ice-bath ultrasonic 4h at 20KHz to be utilized at 15 DEG C, is dispersed with stirring 4h,
1000rpm is centrifuged 90min, obtains the graphene of quaternary ammoniated lignin stable dispersion and the dispersion liquid of carbon nanotube, dispersion liquid is molten
Degree is 5mg/ml.
(3) water of the graphene/carbon nano-tube dispersion liquid and 4.25 mass parts that disperse the quaternary ammoniated lignin of 2 mass parts
After property curing agent DY-175 is mixed evenly, the aqueous epoxy resins DY-128-50 of 5 mass parts is added, E51, in room temperature
Lower mechanical stirring is uniformly mixed, the ultrasonic disperse 10min under 20KHz in supersonic cleaning machine, under vacuum drying oven condition of ice bath, very
Empty pump bubble removing；After bubble eliminates, the coating of 30 μ m-thicks is painted on Q235 carbon steel using spin coating instrument.Solidify under room temperature
5h obtains the graphene/carbon nano-tube base composite anti-corrosive coating of the quaternary ammoniated lignin dispersion.
Quaternary ammoniated lignin dispersed graphite alkene manufactured in the present embodiment/carbon nanotube base composite anti-corrosive coating ZF=0.01HZ
=0.96 × 107Ω/cm；Detection method is the same as embodiment 2.
Embodiment 5
The present embodiment provides a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating preparation sides
Method.
(1) sodium hydrate solid is added in 45ml deionized water, obtains using purification drying is preceding carried out by sodium lignin sulfonate
To the sodium hydroxide solution of 20wt.%, sodium lignin sulfonate is added, obtains what the sodium hydroxide that concentration is 0.3g/mL dissolved
Lignin sulfonic acid sodium solution, ultrasonic disperse 15min.According to quality than sodium lignin sulfonate: the chloro- 2- Hydroxyproyl Trimethyl chlorination of 3-
3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution (60wt.%) is added dropwise to above-mentioned wood by ammonium salt solution=1:0.83 proportion
In quality aqueous slkali, it is stirred to react 6h at 85 DEG C, after completion of the reaction, is cooled to room temperature, obtains reaction solution, by reaction solution
With the bag filter dialysis purification of 1000 molecular weight, the reaction solution after dialysis dries 48h with freeze drier, obtains dark brown quaternary amine
The lignin of change；
(2) by quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 5mg/ml is obtained, it will
The graphene of physical method removing and the multi-arm carbon nano-tube of 2.5 mass parts of 2.5 mass parts are added to the quaternary ammoniated of 10 mass parts
Lignin disperses in aqueous solution, supersonic wave cleaning machine ice-bath ultrasonic 4h at 20KHz to be utilized at 15 DEG C, is dispersed with stirring 4h,
1000rpm is centrifuged 90min, obtains the graphene of quaternary ammoniated lignin stable dispersion and the dispersion liquid of carbon nanotube, dispersion liquid is molten
Degree is 5mg/ml.
(3) water of the graphene/carbon nano-tube dispersion liquid and 4.25 mass parts that disperse the quaternary ammoniated lignin of 2 mass parts
After property curing agent DY-175 is mixed evenly, the aqueous epoxy resins DY-128-50 of 5 mass parts is added, E51, in room temperature
Lower mechanical stirring is uniformly mixed, the ultrasonic disperse 10min under 20KHz in supersonic cleaning machine, under vacuum drying oven condition of ice bath, very
Empty pump bubble removing；After bubble eliminates, the coating of 25 μ m-thicks is painted on Q235 carbon steel using spin coating instrument.Solidify under room temperature
5h obtains the graphene/carbon nano-tube base composite anti-corrosive coating of the quaternary ammoniated lignin dispersion.
Quaternary ammoniated lignin dispersed graphite alkene manufactured in the present embodiment/carbon nanotube base composite anti-corrosive coating ZF=0.01HZ
=2.10 × 107Ω/cm；Detection method is the same as embodiment 2.
Embodiment 6
The present embodiment provides a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating preparation sides
Method.
(1) sodium hydrate solid is added in 45ml deionized water, obtains using purification drying is preceding carried out by alkali lignin
The sodium hydroxide solution of 20wt.%, adds alkali lignin, and it is wooden to obtain the alkali that the sodium hydroxide that concentration is 0.16g/mL dissolves
Plain solution, ultrasonic disperse 15min.According to quality than alkali lignin: 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution=1:0.83
Proportion, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution (60wt.%) is added dropwise in above-mentioned lignin aqueous slkali,
It is stirred to react 6h at 100 DEG C, after completion of the reaction, is cooled to room temperature, obtains reaction solution, by 1000 molecular weight of reaction solution
Bag filter dialysis purification, reaction solution after the dialysis dry 48h of freeze drier obtains the quaternary ammoniated lignin of dark brown；
(2) by quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 10mg/ml is obtained,
The hydroxylating multi-arm carbon nano-tube of graphene and 3 mass parts that the physical method of 2 mass parts is removed is added to the season of 10 mass parts
Aminated lignin disperses in aqueous solution, supersonic wave cleaning machine ice-bath ultrasonic 6h at 20KHz to be utilized at 15 DEG C, is dispersed with stirring
4h, 1000rpm are centrifuged 90min, obtain the graphene of quaternary ammoniated lignin stable dispersion and the dispersion liquid of carbon nanotube, dispersion liquid
Solubility is 5mg/ml.
(3) water of the graphene/carbon nano-tube dispersion liquid and 4.25 mass parts that disperse the quaternary ammoniated lignin of 1 mass parts
After property curing agent DY-175 is mixed evenly, the aqueous epoxy resins DY-128-50 of 5 mass parts is added, E51, in room temperature
Lower mechanical stirring is uniformly mixed, the ultrasonic disperse 10min under 20KHz in supersonic cleaning machine, under vacuum drying oven condition of ice bath, very
Empty pump bubble removing；After bubble eliminates, the coating of 25 μ m-thicks is painted on Q235 carbon steel using spin coating instrument.Solidify under room temperature
8h obtains the graphene/carbon nano-tube base composite anti-corrosive coating of the quaternary ammoniated lignin dispersion.
Quaternary ammoniated lignin dispersed graphite alkene manufactured in the present embodiment/carbon nanotube base composite anti-corrosive coating ZF=0.01HZ
=1.76 × 107Ω/cm；Detection method is the same as embodiment 2.
Embodiment 7
The present embodiment provides a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating preparation sides
Method.
(1) sodium hydrate solid is added in 45ml deionized water, obtains using purification drying is preceding carried out by alkali lignin
The sodium hydroxide solution of 20wt.%, adds alkali lignin, and it is wooden to obtain the alkali that the sodium hydroxide that concentration is 0.16g/mL dissolves
Plain solution, ultrasonic disperse 15min.According to quality than alkali lignin: 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution=1:0.83
Proportion, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution (60wt.%) is added dropwise in above-mentioned lignin aqueous slkali,
It is stirred to react 4h at 85 DEG C, after completion of the reaction, is cooled to room temperature, obtains reaction solution, by 1000 molecular weight of reaction solution
Bag filter dialysis purification, reaction solution after the dialysis dry 48h of freeze drier obtains the quaternary ammoniated lignin of dark brown；
(2) by quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 5mg/ml is obtained, it will
The redox graphene of 2 mass parts and the single armed carbon nanotube of 3 mass parts are added to the quaternary ammoniated lignin dispersion of 5 mass parts
In aqueous solution, supersonic wave cleaning machine ice-bath ultrasonic 6h at 20KHz is utilized at 15 DEG C, is dispersed with stirring 4h, 1000rpm centrifugation
90min, obtains the graphene of quaternary ammoniated lignin stable dispersion and the dispersion liquid of carbon nanotube, and dispersion liquid solubility is 5mg/ml.
(3) water of the graphene/carbon nano-tube dispersion liquid and 4.2 mass parts that disperse the quaternary ammoniated lignin of 1 mass parts
After property curing agent DY-175 is mixed evenly, the aqueous epoxy resins DY-128-50 of 5 mass parts is added, E51, in room temperature
Lower mechanical stirring is uniformly mixed, the ultrasonic disperse 10min under 20KHz in supersonic cleaning machine, under vacuum drying oven condition of ice bath, very
Empty pump bubble removing；After bubble eliminates, the coating of 20 μ m-thicks is painted on a glass using spin coating instrument.Solidify under room temperature
4h obtains the graphene/carbon nano-tube base composite anti-corrosive coating of the quaternary ammoniated lignin dispersion.
Quaternary ammoniated lignin dispersed graphite alkene manufactured in the present embodiment/carbon nanotube base composite anti-corrosive coating ZF=0.01HZ
=1.52 × 107Ω/cm；Detection method is the same as embodiment 2.
Embodiment 8
The present embodiment provides a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating preparation sides
Method.
(1) sodium hydrate solid is added in 45ml deionized water, obtains using purification drying is preceding carried out by alkali lignin
The sodium hydroxide solution of 20wt.%, adds alkali lignin, and it is wooden to obtain the alkali that the sodium hydroxide that concentration is 0.2g/mL dissolves
Plain solution, ultrasonic disperse 15min.According to quality than alkali lignin: 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution=1:0.83
Proportion, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution (60wt.%) is added dropwise in above-mentioned lignin aqueous slkali,
It is stirred to react 5h at 90 DEG C, after completion of the reaction, is cooled to room temperature, obtains reaction solution, by 900 molecular weight of reaction solution
Bag filter dialysis purification, the reaction solution dry 48h of freeze drier after dialysis, obtains the quaternary ammoniated lignin of dark brown；
(2) by quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 15mg/ml is obtained,
The multi-arm carbon nano-tube of the vapour deposition process graphene of 2 mass parts and 3 mass parts is added to the quaternary ammoniated wooden of 10 mass parts
Element dispersion in aqueous solution, supersonic wave cleaning machine ice-bath ultrasonic 6h at 20KHz is utilized at 15 DEG C, is dispersed with stirring 4h,
1000rpm is centrifuged 90min, obtains the graphene of quaternary ammoniated lignin stable dispersion and the dispersion liquid of carbon nanotube, dispersion liquid is molten
Degree is 5mg/ml.
(3) water of the graphene/carbon nano-tube dispersion liquid and 4.5 mass parts that disperse the quaternary ammoniated lignin of 1 mass parts
After property curing agent DY-175 is mixed evenly, the aqueous epoxy resins DY-128-50 of 4.75 mass parts is added, E51, in room
The lower mechanical stirring of temperature is uniformly mixed, the ultrasonic disperse 10min under 20KHz in supersonic cleaning machine, under vacuum drying oven condition of ice bath,
Vacuum extracts bubble；After bubble eliminates, the coating of 45 μ m-thicks is painted on aluminium flake using spin coating instrument.Solidify under room temperature
8h obtains the graphene/carbon nano-tube base composite anti-corrosive coating of the quaternary ammoniated lignin dispersion.
Quaternary ammoniated lignin dispersed graphite alkene manufactured in the present embodiment/carbon nanotube base composite anti-corrosive coating ZF=0.01HZ
=1.40 × 107Ω/cm；Detection method is the same as embodiment 2.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating preparation method, which is characterized in that
The following steps are included:
(1) preparation of quaternary ammoniated lignin
By lignin dissolution in sodium hydroxide solution, ultrasonic disperse obtains lignin dispersion liquid, then that quaternary amine is added dropwise is molten
Liquid reacts under the conditions of heating and stirring, is cooled to room temperature, obtains reaction solution, by reaction solution dialysis purification, drying
Afterwards, quaternary ammoniated lignin is obtained；
(2) preparation of quaternary ammoniated lignin dispersed graphite alkene/carbon nano tube dispersion liquid
By quaternary ammoniated lignin dissolution Yu Shuizhong, quaternary ammoniated lignin dispersion liquid is obtained, graphene and carbon nanotube is added, is surpassed
Sound removing, is dispersed with stirring, and is centrifuged, the graphene/carbon nano-tube dispersion liquid for the quaternary ammoniated lignin dispersion being saturated；
(3) preparation of composite anti-corrosive coating
Graphene/carbon nano-tube dispersion liquid, waterborne curing agent, aqueous epoxy resins that the quaternary ammoniated lignin of saturation disperses are mixed
It closes uniformly, obtains coating Tooth preparation, deaeration, the surface coated in base material solidifies, and obtains the quaternary ammoniated lignin point
Dissipate graphene/carbon nano-tube base composite water soluble corrosion-inhibiting coating.
2. the preparation of quaternary ammoniated lignin dispersed graphite alkene according to claim 1/carbon nanotube base composite anti-corrosive coating
Method, it is characterised in that:
The concentration of quaternary ammoniated lignin dispersion liquid described in step (2) is 5~15mg/mL；
The gross mass of addition graphene and carbon nanotube described in step (2) is the 1/2 of quaternary ammoniated lignin dispersion liquid quality
~1 times；
The quality of addition graphene and carbon nanotube described in step (2) is graphene: carbon nanotube=1:1~1:4.
3. the preparation of quaternary ammoniated lignin dispersed graphite alkene according to claim 1/carbon nanotube base composite anti-corrosive coating
Method, it is characterised in that:
The graphene/carbon nano-tube dispersion of the quaternary ammoniated lignin dispersion of saturation in coating Tooth preparation described in step (3)
The mass ratio of liquid and aqueous epoxy resins is 1:5~3:5；
The mass ratio of aqueous epoxy resins and waterborne curing agent in coating Tooth preparation described in step (3) is 1:0.8~1:
0.9。
4. the preparation of quaternary ammoniated lignin dispersed graphite alkene according to claim 1/carbon nanotube base composite anti-corrosive coating
Method, it is characterised in that:
Lignin described in step (1) is sodium lignin sulfonate, alkali lignin or high-boiling alcohol lignin；
The concentration of sodium hydroxide solution described in step (1) is 20wt.%；
The concentration of lignin dispersion liquid described in step (1) is 0.16~0.3g/mL；
Quaternary amine salting liquid described in step (1) is 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution, mass concentration 60%；
The mass ratio of lignin and quaternary amine in reaction solution described in step (1) is 1:0.83.
5. the preparation of quaternary ammoniated lignin dispersed graphite alkene according to claim 1/carbon nanotube base composite anti-corrosive coating
Method, it is characterised in that:
Graphene described in step (2) is graphene, chemical method redox graphene or the vapor deposition of physical method removing
Method graphene；
Carbon nanotube described in step (2) is multi-arm carbon nano-tube, single armed carbon nanotube or hydroxylating multi-arm carbon nano-tube；
Aqueous epoxy resins described in step (3) are the epoxy resin that pre-emulsified epoxide number is 51；
Waterborne curing agent described in step (3) is amine curing agent.
6. the preparation of quaternary ammoniated lignin dispersed graphite alkene according to claim 1/carbon nanotube base composite anti-corrosive coating
Method, it is characterised in that:
The temperature of heating described in step (1) is 85~100 DEG C；
When a length of 4~6h of reaction described in step (1)；
Room temperature described in step (1) is 20~40 DEG C；
Dialysis described in step (1) uses molecular weight to carry out for 800~1000 bag filter；
Drying described in step (1) is carried out using freeze drier, drying time 48h；
The method of ultrasound described in step (1) and step (2) is under the conditions of 10~30 DEG C and 20kHz with 100% amplitude
Ice-bath ultrasonic.
7. the preparation of quaternary ammoniated lignin dispersed graphite alkene according to claim 1/carbon nanotube base composite anti-corrosive coating
Method, it is characterised in that:
When a length of 4~6h of ultrasound described in step (2)；
The revolving speed of stirring described in step (2) is 100rpm；
The method of centrifugation described in step (2) is to be centrifuged 90min with 1000rpm.
8. the preparation of quaternary ammoniated lignin dispersed graphite alkene according to claim 1/carbon nanotube base composite anti-corrosive coating
Method, it is characterised in that:
Mixed sequence described in step (3) is first to receive the graphene/carbon that waterborne curing agent and quaternary ammoniated lignin disperse
The mixing of mitron dispersion liquid, adds aqueous epoxy resins；
Uniformly mixed method described in step (3) is 5~15min of ultrasonic disperse at 20KHz, 15~25 DEG C；
The method of deaeration described in step (3) is to be dried in vacuo under condition of ice bath, and vacuum extracts bubble；
Base material described in step (3) is glass plate, aluminium flake or Q235 carbon steel；
Cured condition described in step (3) is to solidify 4~8h at room temperature；
Lignin described in step (3)/graphene-based composite anti-corrosive coating is with a thickness of 20~45 μm.
9. a kind of quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating, it is characterised in that: by claim
Preparation method described in 1~8 obtains.
10. the application of quaternary ammoniated lignin dispersed graphite alkene as claimed in claim 9/carbon nanotube base composite anti-corrosive coating,
Be characterized in that: by the quaternary ammoniated lignin dispersed graphite alkene/carbon nanotube base composite anti-corrosive coating be used for metal base or
The anticorrosion of building material surface.
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