CN110093091A - A kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coating and the preparation method and application thereof - Google Patents
A kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coating and the preparation method and application thereof Download PDFInfo
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- CN110093091A CN110093091A CN201910457238.XA CN201910457238A CN110093091A CN 110093091 A CN110093091 A CN 110093091A CN 201910457238 A CN201910457238 A CN 201910457238A CN 110093091 A CN110093091 A CN 110093091A
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- lignin
- alpha
- quaternary ammoniated
- phosphate
- ammoniated lignin
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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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
Abstract
The invention belongs to the preparation technical fields of metal anti-corrosive paint, and in particular to a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coating and the preparation method and application thereof.This method prepares quaternary ammoniated lignin/alpha zirconium phosphate dispersion liquid using simple ultrasonic treatment, then quaternary ammoniated lignin/alpha zirconium phosphate composite granule is obtained by freeze-drying, it is mixed again with epoxy resin and curing agent, obtains quaternary ammoniated lignin/alpha zirconium phosphate corrosion-resistant epoxy paint.This method uses reproducible biological material lignin, positive and negative charge and interaction of hydrogen bond using the quaternary ammoniated, amphipathic of lignin and its between alpha zirconium phosphate, increase the hydrophobicity of alpha zirconium phosphate, it is uniformly dispersed in epoxy resin, the obtained alpha zirconium phosphate in coating can obstruct the intrusion of corrosion small molecule layer by layer, and lignin enhances corrosion-inhibiting coating and metallic substrates adhesive force, and plays the role of cooperateing with corrosion-resistant, delays the corrosion rate of substrate.
Description
Technical field
The invention belongs to the preparation technical fields of metal anti-corrosive paint, and in particular to a kind of quaternary ammoniated lignin/alpha-phosphate
Zirconium base composite anticorrosion 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.
Metal material is influenced by surrounding medium and generates corrosion, and huge property loss is caused.Widely used anti-corrosion
Method is coating to be coated on to metal surface metal is prevented to contact with the direct of corrosive medium, however use simple coating not
Antisepsis can be played well, therefore usually needs to add antiseptic property of the filler to enhance coating.And alpha zirconium phosphate due to
Its excellent two-dimensional layered structure makes it have good barrier property and plays good antisepsis.
However, making that it is difficult to disperse and its is hydrophilic since there is alpha zirconium phosphate regular two-dimentional crystal form to be not easily stripped
Surface is unfavorable for the promotion of antiseptic property, these reasons all limit its application in hydrophobic 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 provide a kind of quaternary ammoniated lignin/
The preparation method of alpha-phosphate zirconium base composite anticorrosion coating.
It is multiple that another object of the present invention is to provide quaternary ammoniated lignin/alpha-phosphate zirconium bases prepared by the above method
Close anticorrosive paint.
A further object of the present invention is to provide above-mentioned quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coatings to prevent
Application in building material surface corrosion.
A further object of the present invention is to provide a kind of above-mentioned quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coatings
Application method.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coating, comprising the following steps:
(1) preparation of quaternary ammoniated lignin/alpha zirconium phosphate
By quaternary ammoniated lignin dissolution Yu Shuizhong, quaternary ammoniated lignin dispersion liquid is obtained, is then dispersed with alpha zirconium phosphate
After liquid mixing, successively after ultrasound, stirring, centrifugal filtration, it is dried to obtain quaternary ammoniated lignin/alpha zirconium phosphate；
(2) preparation of composite anticorrosion coating
Quaternary ammoniated lignin/alpha zirconium phosphate, epoxy resin and epoxy curing agent are uniformly mixed in a solvent, obtained
Anticorrosive paint.
Lignin described in step (1) is alkali lignin, high-boiling alcohol lignin, organic solvent lignin, sulfate wood
At least one of quality and enzymolysis xylogen.
The preparation step of quaternary ammoniated lignin described in step (1) are as follows:
Lignin is uniformly mixed to obtain lignin aqueous slkali with sodium hydroxide solution, the chloro- 2- hydroxypropyl of 3- is then added
Trimethyl ammonia chloride aqueous ammonium is reacted, and reaction solution is dried to obtain quaternary ammoniated lignin after the reaction was completed.
In the preparation of quaternary ammoniated lignin, the concentration of the sodium hydroxide solution is 10~35wt.%, preferably
20wt.%；The concentration of the lignin aqueous slkali is 0.05~0.5g/mL, preferably 0.15g/mL；The chloro- 2- hydroxypropyl of 3-
The concentration of base trimethyl ammonia chloride aqueous ammonium is 25~80wt.%, preferably 60wt.%；The lignin and the chloro- 2- hydroxypropyl of 3-
The mass ratio of base trimethyl ammonium chloride is 1:0.1~1:5, preferably 1:0.85.
In the preparation of quaternary ammoniated lignin, the lignin is using preceding carrying out purification drying；It is described to be uniformly mixed to pass through
Ultrasonic disperse is mixed, and ultrasonic time is 5~60min, preferably 15min；The 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride
Aqueous solution is added dropwise in lignin aqueous slkali with the speed of 1~10mL/min；The reaction is stirred at 85~100 DEG C
1~10h of reaction is mixed, the reaction time is preferably 4h；It is described to be after the reaction was completed cooled to room temperature reaction solution, it then will react molten
The bag filter dialysis purification of 800~1200 molecular weight of liquid, then the reaction solution after dialysis is freeze-dried 24~72h, obtain depth
The quaternary ammoniated lignin of brown.
The concentration of quaternary ammoniated lignin is 0.5~1.5g/L in quaternary ammoniated lignin dispersion liquid described in step (1).
The preparation step of alpha zirconium phosphate dispersion liquid described in step (1) are as follows:
Alpha zirconium phosphate powder is dispersed in water, tetrabutylammonium hydroxide solution is then added, stirs, is centrifuged after ultrasound
To the alpha zirconium phosphate dispersion liquid of removing.
In the preparation of alpha zirconium phosphate dispersion liquid, the dosage of the alpha zirconium phosphate powder meets the α-that 5~10g is added in every 1L water
Phosphoric acid zirconium powder；The concentration of the tetrabutylammonium hydroxide solution is 10~40wt.%, preferably 25wt.%；The tetrabutyl
The molar ratio of ammonium hydroxide and alpha zirconium phosphate is 1:0.01~1:5；Preferably 1:0.8~1:1.2.
In the preparation of alpha zirconium phosphate dispersion liquid, the ultrasonic agitation handles 0.5 to pass through 10~100% amplitude water bath sonicators
Then~5h stirs 0.5~5h with the speed of 50~1000rpm；Preferably, 1h is handled with 100% amplitude water bath sonicator, then
1h is stirred with the speed of 100rpm；It is described centrifugation for 1000~10000rpm be centrifuged 5~30min, preferably with 5000rpm from
Heart 15min.
Quaternary ammoniated lignin described in step (1) and alpha zirconium phosphate mass ratio are 1:100~5:100.
Ultrasound described in step (1) be 10~40kHz and 15~30 DEG C ultrasound 1~2 hour, supersonic frequency is preferably
20kHz；To be stirred 3~12 hours with the speed of 50~1000rpm, mixing speed is more preferably for step (1) stirring
100rpm；Centrifugation described in step (1) is to be centrifuged 0.5~1.5 hour with the speed of 5000~16000rpm, and centrifugal speed is excellent
It is selected as 10000rpm；Drying described in step (1) is freeze-drying, and drying time is 24~48h.
Step (2) epoxy curing agent be amine curing agent, preferably ethylenediamine, hexamethylene diamine, diethylenetriamine,
At least one of triethylene tetramine and diethylaminopropylamine；More preferably triethylene tetramine；
The epoxide number of epoxy resin described in step (2) is 44~51；
Solvent described in step (2) is acetone, ethyl alcohol, tetrahydrofuran, dimethylbenzene, butanol, in dibutyl ester and isopropanol
It is at least one.
The concentration of quaternary ammoniated lignin/alpha zirconium phosphate is 0.05~0.30mg/mL in step (2) described anticorrosive paint；
The mass ratio of step (2) epoxy curing agent and epoxy resin is 0.1:100~1:50；Preferably 0.5:
100。
The mass ratio of quaternary ammoniated lignin/alpha zirconium phosphate and epoxy resin is in anticorrosive paint described in step (2)
0.5:100~5:100.
Be uniformly mixed described in step (2) for first by the dispersion of quaternary ammoniated lignin/alpha zirconium phosphate in a solvent, then plus
Enter epoxy resin and 30~60min of ultrasonic disperse at 10~40kHz and 15~30 DEG C, then is stirred with the speed of 50~1000rpm
It mixes 1~2 hour, epoxy curing agent is then added and continues 5~30min of stirring；Preferably, supersonic frequency 20kHz, stirring
Speed is 100rpm.
A kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coating prepared by the above method.
Application of the above-mentioned quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coating in the corrosion of anti-building material surface.
A kind of application method of above-mentioned quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coating, specially applies anti-corrosion
It is coated in the surface of base material after material deaeration, quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating is obtained after solidification.
Wherein, the base material is glass plate, aluminium flake or Q235 carbon steel；The condition of cure is in room temperature condition
Lower standing solidification 12~for 24 hours；The quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating is with a thickness of 25~70 μm.
Room temperature of the present invention and unspecified temperature are 15~35 DEG C.
Compared with prior art, the present invention having the following advantages and benefits:
(1) the characteristics of present invention contains a large amount of phenolic hydroxyl group and alcoholic extract hydroxyl group by quaternary ammoniated lignin, amphipathic using its
And positive and negative charge and interaction of hydrogen bond between quaternary ammoniated lignin and alpha zirconium phosphate, so that quaternary ammoniated lignin is to α-phosphorus
Sour zirconium is surface modified, and the hydrophobicity of alpha zirconium phosphate can be changed, so that quaternary ammoniated lignin/alpha zirconium phosphate is uniformly dispersed in
In epoxy resin, and increase the compatibility of alpha zirconium phosphate and epoxy resin, enhances the adhesive force of coating and base metal building materials.
(2) quaternary ammoniated lignin/alpha-phosphate zirconium base composite anticorrosion coating preparation process is simple in the present invention, operability
By force.Since the lignin utilized is reproducible biological material, environmentally protective, cost is relatively low, easy to use.In coating
The alpha zirconium phosphate of high degree of dispersion can obstruct the intrusion of corrosion small molecule layer by layer, greatly reduce corrosion of the small molecule to metallic substrates,
Delay the corrosion rate of substrate.The coating can be widely applied to exposed metal base and other building material surfaces, and extension is protected
The service life of matrix.It shows preferable capacitive reactance arc in electrochemical AC impedance (EIS), at low-limit frequency (0.01Hz)
Impedance modulus (Zf) it is (1.7~9.7) × 106Ω/cm2。
Detailed description of the invention
Fig. 1 is the SEM microscopic appearance figure of gained alpha zirconium phosphate and quaternary ammoniated lignin/alpha zirconium phosphate in embodiment 1；Wherein
Scheming (a) is alpha zirconium phosphate, and figure (b) is quaternary ammoniated lignin/alpha zirconium phosphate.
Fig. 2 is the 1 quaternary ammoniated lignin/α-phosphorus of gained of 1 gained alpha-phosphate zirconium base composite anti-corrosive coating of comparative example and embodiment
The SEM of sour zirconium base composite anti-corrosive coating cross sections schemes；Wherein figure (a) is alpha-phosphate zirconium base composite anti-corrosive coating, and figure (b) is quaternary ammoniated
Lignin/alpha zirconium phosphate composite anti-corrosive coating.
Fig. 3 is the quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating of 1 gained of embodiment and 1 gained α of comparative example-phosphorus
The water contact angle figure of sour zirconium base composite anti-corrosive coating；Wherein figure (a) is that quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive applies
Layer, figure (b) are alpha-phosphate zirconium base composite anti-corrosive coating.
Fig. 4 is AC impedance (EIS) figure of different coating in embodiment 1 and comparative example 1.
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.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Embodiment 1
It is compound anti-that the present embodiment provides a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coatings and alpha-phosphate zirconium base
The preparation method of rotten coating.
(1) after alkali lignin is using purification drying is preceding carried out, sodium hydrate solid addition 45ml deionized water is obtained
Alkali lignin is added in the sodium hydroxide solution of 20wt.%, and obtaining concentration is 0.15g/mL lignin aqueous slkali, ultrasonic disperse
15min.According to quality than alkali lignin: 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride=1:0.85 proportion, by the chloro- 2- hydroxyl of 3-
Hydroxypropyltrimonium chloride aqueous solution (60wt.%) is added dropwise in above-mentioned lignin aqueous slkali, is stirred to react at 85 DEG C
4h is cooled to room temperature after completion of the reaction, obtains reaction solution, by the bag filter dialysis purification of 1000 molecular weight of reaction solution,
The reaction solution dry 48h of freeze drier after dialysis, obtains the quaternary ammoniated lignin of dark brown, and quaternary ammoniated lignin is molten
In Xie Yushui, the quaternary ammoniated lignin dispersion liquid that solubility is 1g/L is obtained.
The dispersion of alpha zirconium phosphate powder is made into its concentration 10g/L in aqueous solution, by tetrabutylammonium hydroxide and alpha-phosphate
The tetrabutylammonium hydroxide solution of 25wt.% is added in zirconium molar ratio 1:1, and 100% amplitude water bath sonicator is handled 1 hour, 100rpm
Stirring 1 hour, 5000rpm centrifugation 15min remove unstripped alpha zirconium phosphate solid, the alpha zirconium phosphate dispersion liquid removed.
Two kinds of dispersion liquids are mixed according to quaternary ammoniated lignin and alpha zirconium phosphate mass ratio 1:100, then the ultrasound 1 at 20kHz and 25 DEG C
Hour, then 100rpm stirring 12 hours, 10000rpm is centrifuged 1 hour, is collected solid gel vacuum freeze drying 48 hours and is obtained
Quaternary ammoniated lignin/alpha zirconium phosphate powder.
(2) quaternary ammoniated lignin/alpha zirconium phosphate dispersion is obtained into dispersion liquid in acetone, makes the concentration of dispersion liquid
0.05mg/mL, by dispersion liquid with e-51 epoxy resin according to the quality of quaternary ammoniated lignin/alpha zirconium phosphate and e-51 epoxy resin
Than for 0.5:100 mixing, in 20kHz and 25 DEG C of ultrasound 30min, 100rpm stirring 1 hour is added and epoxy resin mass ratio
For 7:100 triethylene tetramine curing agent be mixed 15min be uniformly mixed obtain anticorrosive paint, in vacuum drying oven, vacuum
Abstraction bubble obtains anticorrosive paint；Anticorrosive paint is painted to the coating of 45 μ m-thicks using spin coating instrument on Q235 carbon steel.Room temperature item
Solidify 12h under part, obtains the quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating.
Scanning electron microscope is respectively adopted and microscopic appearance point is carried out to above-mentioned alpha zirconium phosphate, quaternary ammoniated lignin/alpha zirconium phosphate
Analysis.Fig. 1 is the SEM microscopic appearance figure of gained alpha zirconium phosphate and quaternary ammoniated lignin/alpha zirconium phosphate in embodiment 1；Wherein scheme (a)
For alpha zirconium phosphate, scheming (b) is quaternary ammoniated lignin/alpha zirconium phosphate.It can be seen that it is quaternary ammoniated it is lignin-modified after alpha zirconium phosphate it is brilliant
Body surface face is significantly roughening, and uniformly middle compatibility is good in matrix epoxy resin dispersion.
Embodiment 2
The present embodiment provides a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating preparation methods.
(1) sodium hydrate solid is added in 45ml deionized water, obtains using purification drying is preceding carried out by high boiling Vinsol
To the sodium hydroxide solution of 20wt.%, alkali lignin is added, obtains the wooden of the sodium hydroxide dissolution that concentration is 0.15g/mL
Plain aqueous slkali, ultrasonic disperse 15min.According to quality than alkali lignin: 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride=1:0.85
Proportion, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous 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,
By quaternary ammoniated lignin dissolution Yu Shuizhong, the quaternary ammoniated lignin dispersion liquid that solubility is 1g/L is obtained.
The dispersion of alpha zirconium phosphate powder is made into its concentration 10g/L in aqueous solution, by tetrabutylammonium hydroxide and alpha-phosphate
The tetrabutylammonium hydroxide solution of 25wt.% is added in zirconium molar ratio 1:1, and 100% amplitude water bath sonicator is handled 1 hour, 100rpm
Stirring 1 hour, 5000rpm centrifugation 15min remove unstripped alpha zirconium phosphate solid, the alpha zirconium phosphate dispersion liquid removed.
Two kinds of dispersion liquids are mixed according to quaternary ammoniated lignin and alpha zirconium phosphate mass ratio 1:100, then the ultrasound 1 at 20kHz and 25 DEG C
Hour, then 100rpm stirring 12 hours, 10000rpm is centrifuged 1 hour, is collected solid gel vacuum freeze drying 48 hours and is obtained
Quaternary ammoniated lignin/alpha zirconium phosphate powder.
(2) quaternary ammoniated lignin/alpha zirconium phosphate dispersion is obtained into dispersion liquid in acetone, makes the concentration of dispersion liquid
0.05mg/mL, by dispersion liquid with e-51 epoxy resin according to the quality of quaternary ammoniated lignin/alpha zirconium phosphate and e-51 epoxy resin
Than for 0.5:100 mixing, the then ultrasound 30min at 20kHz and 25 DEG C, 100rpm stirring 1 hour is added and epoxy resin
The triethylene tetramine curing agent mixing 15min that mass ratio is 7:100, which is uniformly mixed, to be obtained, under the conditions of vacuum drying oven, very
Empty pump bubble removing anticorrosive paint；Anticorrosive paint is painted to the coating of 45 μ m-thicks using spin coating instrument on Q235 carbon steel.Room temperature condition
Lower solidification 12h obtains the quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating.
Embodiment 3
The present embodiment provides a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating preparation methods.
(1) the identical method of embodiment 1 is taken in the preparation of quaternary ammoniated lignin/alpha zirconium phosphate
(2) quaternary ammoniated lignin/alpha zirconium phosphate dispersion is obtained into dispersion liquid in acetone, dispersion liquid is made to obtain concentration
0.05mg/mL, by dispersion liquid with e-51 epoxy resin according to the quality of quaternary ammoniated lignin/alpha zirconium phosphate and e-51 epoxy resin
Than mixing for 2:100, then the ultrasound 30min at 20kHz and 25 DEG C, 100rpm are stirred 1 hour, are added and asphalt mixtures modified by epoxy resin lipid
Amount is uniformly mixed than the triethylene tetramine curing agent mixing 15min for being 7:100, under the conditions of vacuum drying oven, vacuum abstraction
Bubble obtains anticorrosive paint；Anticorrosive paint is painted to the coating of 45 μ m-thicks using spin coating instrument on Q235 carbon steel.Under room temperature
Solidify 12h, obtains the quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating.
Embodiment 4
The present embodiment provides a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating preparation methods.
(1) the identical method of embodiment 1 is taken in the preparation of quaternary ammoniated lignin/alpha zirconium phosphate.
(2) in acetone by quaternary ammoniated lignin/alpha zirconium phosphate dispersion, so that dispersion liquid is obtained concentration 0.05mg/mL, will divide
Dispersion liquid is that 5:100 is mixed with the mass ratio of e-51 epoxy resin according to quaternary ammoniated lignin/alpha zirconium phosphate with e-51 epoxy resin,
Then the ultrasound 30min at 20kHz and 25 DEG C, 100rpm are stirred 1 hour, and adding with epoxy resin mass ratio is 7:100's
Triethylene tetramine curing agent is mixed 15min and is uniformly mixed, and under the conditions of vacuum drying oven, vacuum abstraction bubble obtains anti-corrosion painting
Material；Anticorrosive paint is painted to the coating of 45 μ m-thicks using spin coating instrument on Q235 carbon steel.Solidify 12h under room temperature, obtains institute
The quaternary ammoniated lignin stated/alpha-phosphate zirconium base composite anti-corrosive coating.
Embodiment 5
The present embodiment provides a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating preparation methods.
(1) quaternary ammoniated lignin dispersion liquid and alpha zirconium phosphate dispersion liquid are prepared using the method for embodiment 1.According to quaternary ammoniated
Lignin and alpha zirconium phosphate mass ratio 2.5:100 mix two kinds of dispersion liquids, then ultrasound 1 hour at 20kHz and 25 DEG C, then
100rpm is stirred 12 hours, and 10000rpm is centrifuged 1 hour, is collected solid gel vacuum freeze drying 48 hours and is obtained quaternary ammoniated wood
Quality/alpha zirconium phosphate powder.
(2) in acetone by quaternary ammoniated lignin/alpha zirconium phosphate dispersion, dispersion liquid is made to obtain concentration 0.05mg/mL, according to
The quality of alpha zirconium phosphate is that 0.5:100 is mixed with the mass ratio of e-51 epoxy resin in dispersion liquid, then at 20kHz and 25 DEG C
Ultrasonic 30min, 100rpm are stirred 1 hour, are added and are mixed with epoxy resin mass ratio for the triethylene tetramine curing agent of 7:100
It stirs 15min to be uniformly mixed, under the conditions of vacuum drying oven, vacuum abstraction bubble obtains anticorrosive paint；Using spin coating instrument by anti-corrosion
Coating paints the coating of 45 μ m-thicks on Q235 carbon steel.Solidify 12h under room temperature, obtains the quaternary ammoniated lignin/α-
Phosphoric acid zirconium base composite anti-corrosive coating.
Embodiment 6
The present embodiment provides a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating preparation methods.
(1) quaternary ammoniated lignin dispersion liquid and alpha zirconium phosphate dispersion liquid are prepared using the method for embodiment 1.According to quaternary ammoniated
Lignin and alpha zirconium phosphate mass ratio 5:100 mix two kinds of dispersion liquids, then ultrasound 1 hour at 20kHz and 25 DEG C, then
100rpm is stirred 12 hours, and 10000rpm is centrifuged 1 hour, is collected solid gel vacuum freeze drying 48 hours and is obtained quaternary ammoniated wood
Quality/alpha zirconium phosphate powder.
(2) quaternary ammoniated lignin/alpha zirconium phosphate dispersion is obtained into dispersion liquid in acetone, makes the concentration of dispersion liquid
0.05mg/mL, by dispersion liquid with e-51 epoxy resin according to the quality of quaternary ammoniated lignin/alpha zirconium phosphate and e-51 epoxy resin
Than for 0.5:100 mixing, the then ultrasound 30min at 20kHz and 25 DEG C, 100rpm stirring 1 hour is added and epoxy resin
The triethylene tetramine curing agent that mass ratio is 7:100 is mixed 15min and is uniformly mixed, and under the conditions of vacuum drying oven, vacuum is taken out
Bubble removing obtains anticorrosive paint；Anticorrosive paint is painted to the coating of 45 μ m-thicks using spin coating instrument on Q235 carbon steel.Room temperature condition
Lower solidification 12h obtains the quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating.
Embodiment 7
The present embodiment provides a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating preparation methods.
(1) the identical method of embodiment 1 is taken in the preparation of quaternary ammoniated lignin/alpha zirconium phosphate.
(2) quaternary ammoniated lignin/alpha zirconium phosphate dispersion is obtained into dispersion liquid in acetone, makes the concentration of dispersion liquid
0.15mg/mL, by dispersion liquid with e-51 epoxy resin according to the quality of quaternary ammoniated lignin/alpha zirconium phosphate and e-51 epoxy resin
Than mixing for 5:100, then the ultrasound 30min at 20kHz and 25 DEG C, 100rpm are stirred 1 hour, are added and asphalt mixtures modified by epoxy resin lipid
Amount is uniformly mixed than the triethylene tetramine curing agent mixing 15min for being 7:100, and in vacuum drying oven, vacuum extracts bubble
Obtain anticorrosive paint；Anticorrosive paint is painted to the coating of 45 μ m-thicks using spin coating instrument on Q235 carbon steel.Solidify under room temperature
12h obtains the quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating.
Embodiment 8
The present embodiment provides a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating preparation methods.
(1) the identical method of embodiment 1 is taken in the preparation of quaternary ammoniated lignin/alpha zirconium phosphate.
(2) quaternary ammoniated lignin/alpha zirconium phosphate dispersion is obtained into dispersion liquid in acetone, dispersion liquid is made to obtain concentration
0.3mg/mL, by dispersion liquid with e-51 epoxy resin according to the quality of quaternary ammoniated lignin/alpha zirconium phosphate and e-51 epoxy resin
Than mixing for 5:100, then the ultrasound 30min at 20kHz and 25 DEG C, 100rpm are stirred 1 hour, are added and asphalt mixtures modified by epoxy resin lipid
Amount is uniformly mixed than the triethylene tetramine curing agent mixing 15min for being 7:100, under the conditions of vacuum drying oven, vacuum abstraction
Bubble obtains anticorrosive paint；Anticorrosive paint is painted to the coating of 45 μ m-thicks using spin coating instrument on Q235 carbon steel.Under room temperature
Solidify 12h, obtains the quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating.
Comparative example 1
(1) preparation of e-51 epoxy resin (EP) corrosion-inhibiting coating:
According to the additional amount of acetone and e-51 epoxy resin in (2) the step of embodiment 1, acetone is added in extracting epoxy resin
In, then the ultrasound 30min at 20kHz and 25 DEG C, 100rpm are stirred 1 hour, and adding with epoxy resin mass ratio is 7:100
Triethylene tetramine curing agent be mixed 15min be uniformly mixed, under the conditions of vacuum drying oven, vacuum abstraction bubble obtain anti-corrosion
Coating；Anticorrosive paint is painted to the coating of 45 μ m-thicks using spin coating instrument on Q235 carbon steel.Solidify 12h under room temperature, obtains
The e-51 epoxy resin corrosion-inhibiting coating.
(2) preparation of alpha-phosphate zirconium base composite anti-corrosive coating:
Alpha zirconium phosphate dispersion is obtained into dispersion liquid in acetone, dispersion liquid is made to obtain concentration 0.05mg/mL, by dispersion liquid and
E-51 epoxy resin is that 0.5:100 is mixed with the mass ratio of e-51 epoxy resin according to alpha zirconium phosphate, then at 20kHz and 25 DEG C
Lower ultrasound 30min, 100rpm are stirred 1 hour, are added mixed for the triethylene tetramine curing agent of 7:100 with epoxy resin mass ratio
It closes stirring 15min to be uniformly mixed, under the conditions of vacuum drying oven, vacuum extracts bubble；Anticorrosive paint is obtained after bubble eliminates, benefit
Anticorrosive paint is painted to the coating of 45 μ m-thicks with spin coating instrument on Q235 carbon steel.Solidify 12h under room temperature, obtains the α-
Phosphoric acid zirconium base composite anti-corrosive coating.
Fig. 2 is the 1 quaternary ammoniated lignin/α-phosphorus of gained of 1 gained alpha-phosphate zirconium base composite anti-corrosive coating of comparative example and embodiment
The SEM of sour zirconium base composite anti-corrosive coating cross sections schemes.Fig. 3 is the 1 quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive of gained of embodiment
The water contact angle figure of 1 gained alpha-phosphate zirconium base composite anti-corrosive coating of coating and comparative example.It can be seen by the comparison of Fig. 3 water contact angle
Out, the addition of quaternary ammoniated lignin is so that the hydrophobicity of corrosion-inhibiting coating increases, more conducively anti-corrosion.
Study the electrochemical anti-corrosive performance of coating at room temperature with model CHI660 electrochemical workstation.Wherein, with band
The saturated calomel electrode for having Luggin capillary is reference electrode, and platinum plate electrode is to electrode, with the quaternary ammoniated wood of the preparation of embodiment 1
Quality/alpha-phosphate zirconium base composite anti-corrosive coating, e-51 epoxy coating and alpha-phosphate zirconium base composite anti-corrosive prepared by comparative example 1
Coating, uncoated coating Q235 carbon steel respectively as working electrode, be immersed in the simulated seawater of 3.5wt%NaCl for 24 hours, make
After open circuit potential (OCP) is stablized, with sine wave disturbance amplitude 20mV at OCP, frequency is that 100000Hz~0.01Hz carries out electricity
Chemical impedance composes (EIS) scanning.
As a result as shown in Figure 4, it can be seen that quaternary ammoniated lignin/alpha zirconium phosphate composite anti-corrosive coating is obviously than pure epoxy
Resinous coat and alpha-phosphate zirconium base composite anti-corrosive coating performance are excellent, when lowest frequency (0.01Hz), epoxy resin anti-corrosion
The Z of coatingf=3.5 × 103Ω/cm2, the Z of alpha-phosphate zirconium base composite anti-corrosive coatingf=4.1 × 104Ω/cm2, and quaternary ammoniated wood
Quality/alpha-phosphate zirconium base composite anti-corrosive coating is Zf=1.7 × 106Ω/cm2.Due to the modulus of impedance at low-limit frequency (0.01Hz)
Amount can use the semiquantitative index of making coatings barrier property, therefore illustrate quaternary ammoniated lignin/alpha-phosphate zirconium base prepared by embodiment 1
Composite anti-corrosive coating has best Corrosion Protection.
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/alpha-phosphate zirconium base composite anticorrosion coating preparation method, which is characterized in that including following step
It is rapid:
(1) preparation of quaternary ammoniated lignin/alpha zirconium phosphate
By quaternary ammoniated lignin dissolution Yu Shuizhong, quaternary ammoniated lignin dispersion liquid is obtained, it is then mixed with alpha zirconium phosphate dispersion liquid
After conjunction, successively after ultrasound, stirring, centrifugal filtration, it is dried to obtain quaternary ammoniated lignin/alpha zirconium phosphate；
(2) preparation of composite anticorrosion coating
Quaternary ammoniated lignin/alpha zirconium phosphate, epoxy resin and epoxy curing agent are uniformly mixed in a solvent, obtain anti-corrosion
Coating.
2. quaternary ammoniated lignin according to claim 1/alpha-phosphate zirconium base composite anticorrosion coating preparation method, feature
It is:
Lignin described in step (1) is alkali lignin, high-boiling alcohol lignin, organic solvent lignin, sulfate-reducing conditions
At least one of with enzymolysis xylogen；
The concentration of quaternary ammoniated lignin is 0.5~1.5g/L in quaternary ammoniated lignin dispersion liquid described in step (1)；
Quaternary ammoniated lignin described in step (1) and alpha zirconium phosphate mass ratio are 1:100~5:100.
3. quaternary ammoniated lignin according to claim 1 or 2/alpha-phosphate zirconium base composite anticorrosion coating preparation method,
It is characterized in that:
The preparation step of quaternary ammoniated lignin described in step (1) are as follows: be uniformly mixed lignin with sodium hydroxide solution
To lignin aqueous slkali, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution is then added, it is after the reaction was completed that reaction solution is dry
Obtain quaternary ammoniated lignin；
The preparation step of alpha zirconium phosphate dispersion liquid described in step (1) are as follows: alpha zirconium phosphate powder is dispersed in water, then plus
Enter tetrabutylammonium hydroxide solution, stirred after ultrasound, is centrifuged the alpha zirconium phosphate dispersion liquid removed.
4. quaternary ammoniated lignin according to claim 3/alpha-phosphate zirconium base composite anticorrosion coating preparation method, feature
It is:
In the preparation step of quaternary ammoniated lignin, the concentration of the sodium hydroxide solution is 10~35wt.%；The lignin alkali
The concentration of solution is 0.05~0.5g/mL；The concentration of the 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution be 25~
80wt.%；The mass ratio of the lignin and 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is 1:0.1~1:5；
In the preparation step of quaternary ammoniated lignin, the reaction is to be stirred to react 1~10h at 85~100 DEG C；It is described to have reacted
Reaction solution is cooled to room temperature by Cheng Hou, then by the bag filter dialysis purification of 800~1200 molecular weight of reaction solution, then will
Reaction solution after dialysis is freeze-dried 24~72h, obtains the quaternary ammoniated lignin of dark brown.
5. quaternary ammoniated lignin according to claim 1/alpha-phosphate zirconium base composite anticorrosion coating preparation method, feature
It is:
Ultrasound described in step (1) be 10~40kHz and 15~30 DEG C ultrasound 1~2 hour；
Step (1) stirring is with the speed of 50~1000rpm stirring 3~12 hours；
Centrifugation described in step (1) is to be centrifuged 0.5~1.5 hour with the speed of 5000~16000rpm；
Drying described in step (1) is freeze-drying, and drying time is 24~48h.
6. quaternary ammoniated lignin according to claim 1/alpha-phosphate zirconium base composite anticorrosion coating preparation method, feature
It is:
Step (2) epoxy curing agent is amine curing agent；
The epoxide number of epoxy resin described in step (2) is 44~51；
Solvent described in step (2) is acetone, ethyl alcohol, tetrahydrofuran, dimethylbenzene, butanol, in dibutyl ester and isopropanol at least
It is a kind of.
7. quaternary ammoniated lignin according to claim 1/alpha-phosphate zirconium base composite anticorrosion coating preparation method, feature
It is:
The concentration of quaternary ammoniated lignin/alpha zirconium phosphate is 0.05~0.30mg/mL in step (2) described anticorrosive paint；
The mass ratio of step (2) epoxy curing agent and epoxy resin is 0.1:100~1:50；
The mass ratio of quaternary ammoniated lignin/alpha zirconium phosphate and epoxy resin is 0.5:100 in anticorrosive paint described in step (2)
~5:100；
It is uniformly mixed described in step (2) first to disperse quaternary ammoniated lignin/alpha zirconium phosphate in a solvent, ring to be then added
Oxygen resin and 30~60min of ultrasonic disperse at 10~40kHz, 15~30 DEG C, then 1~2 is stirred with the speed of 50~1000rpm
Hour, epoxy curing agent is then added and continues 5~30min of stirring.
8. a kind of quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive of the method preparation of any one according to claim 1~7
Coating.
9. aminated lignin according to claim 8/alpha-phosphate zirconium base composite anticorrosion coating is preventing building material surface anti-corrosion
In application.
10. a kind of aminated lignin/alpha-phosphate zirconium base composite anticorrosion coating application method according to claim 9, special
Sign is, specific steps are as follows:
It will be coated in the surface of base material after anticorrosive paint deaeration, it is multiple that quaternary ammoniated lignin/alpha-phosphate zirconium base is obtained after solidification
Close corrosion-inhibiting coating；
Wherein, the base material is glass plate, aluminium flake or Q235 carbon steel；The cured condition is at room temperature
Solidification 12~for 24 hours；The quaternary ammoniated lignin/alpha-phosphate zirconium base composite anti-corrosive coating is with a thickness of 25~70 μm.
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