CN109161340A - A kind of environmental friendly, anti-corrosive composite coating - Google Patents
A kind of environmental friendly, anti-corrosive composite coating Download PDFInfo
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- CN109161340A CN109161340A CN201810674491.6A CN201810674491A CN109161340A CN 109161340 A CN109161340 A CN 109161340A CN 201810674491 A CN201810674491 A CN 201810674491A CN 109161340 A CN109161340 A CN 109161340A
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- 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
- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- 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
- C08K2003/329—Phosphorus containing acids
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The present invention relates to paint fields, and more particularly to a kind of environmental friendly, anti-corrosive composite coating, meter by weight includes following components: 100-150 parts of resin binder, 10-15 parts of aqueous polyanion class anticorrosive additive, and 2-10 parts of deionized water；Wherein the resin binder is raw lacquer or water-base resin, the aqueous polyanion class anticorrosive additive includes polyaniline or polyaniline derivative, the aqueous polyanion class anticorrosive additive further includes modifying agent, and the modifying agent is sodium lignin sulfonate, phosphoric acid and ammonium persulfate.The beneficial effects of the present invention are: the composite anticorrosion coating by adding aqueous polyanion class anticorrosive additive in raw lacquer or water-base resin has excellent antiseptic property, while the coating height divides admittedly and low VOC, is a kind of environmentally protective anti-corrosion composite coating.
Description
Technical field
The present invention relates to paint fields, more particularly to a kind of environmental friendly, anti-corrosive composite coating.
Background technique
Metal material has irreplaceable weight as one of construction industry, manufacturing industry and basic material of various heavy industry
It acts on.When metal material is exposed in certain environment (such as temperature, humidity, the pH value of environment), metal and ambient enviroment are just
Chemical or electrochemical reaction can occur, so that the process that metal material is destroyed and consumed occur.Metal erosion is metal material
Existing problem the most serious, it is prevalent in national defense construction and development of the national economy field, seriously restricts metal
Operation strategies and service life directly or indirectly cause huge national economy to lose.According to ASSOCIATE STATISTICS, the whole world is because of corrosion
And general 100,000,000 tons of the metal scrapped, account for about the 20-40% of annual output, economic loss accounts for gross national product (GDP)
4.2%.It is constantly progressive with industrialized, the etching problem got worse causes the concern of each area research personnel.
In order to mitigate and slow down corrosion process, metal surface is coating to apply protective coating to completely cut off and air or corrosive medium
Contact, wherein organic composite coating be widely used in protect metal anticorrosive coating.This type coating is in metal and corruption
Physical barriers are provided between corrosion medium, to protect metal surface；And it is doped with functional anti-corrosion in the coating to fill out
Material, improves the corrosion resistance of coating.Wherein, conductive polymer polyanaline (PANI), due to anodic protection, chemical oxygen
Change reducing power, chemical stability, the anti-corrosion that non-toxic and environment friendly etc. has been proposed as metal protective coating inhibits
Agent, molecular structure show extensive pi-electron non-localized and play effect with protective coating.But due to the dissolubility pole of PANI
Difference, therefore it applies critical constraints in acidic environment as corrosion inhibiter.
Therefore it when developing new composite anticorrosion coating, improves the dissolubility of anticorrosive packing while to reduce volatility organic molten
The use of agent (VOC) is to prepare the hot spot that the environmentally friendly coating of one kind increasingly becomes research.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of includes adding by the polyaniline compound anti-corrosion of dispersing agent of water
The environmental friendly, anti-corrosive composite coating of agent.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
A kind of environmental friendly, anti-corrosive composite coating, by weight meter include following components:
100-150 parts of resin binder, 10-15 parts of aqueous polyanion class anticorrosive additive, 2-10 parts of deionized water；
Wherein the resin binder is raw lacquer or water-base resin, and the aqueous polyanion class anticorrosive additive includes polyaniline
Or polyaniline derivative, the aqueous polyanion class anticorrosive additive further includes modifying agent, and the modifying agent is lignin sulfonic acid
Sodium, phosphoric acid and ammonium persulfate.
The beneficial effects of the present invention are: by adding aqueous polyanion class anticorrosive additive in raw lacquer or water-base resin
Composite anticorrosion coating, there is excellent antiseptic property, while the coating height divides admittedly and low VOC, is a kind of environmentally protective anti-
Rotten composite coating.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained below in conjunction with embodiment.
The most critical design of the present invention is: obtained by adding modified aqueous polyanion class anticorrosive additive
Composite anticorrosion coating has excellent antiseptic property, while the coating height divides admittedly and low VOC, environmentally protective.
A kind of environmental friendly, anti-corrosive composite coating, by weight meter include following components:
100-150 parts of resin binder, 10-15 parts of aqueous polyanion class anticorrosive additive, 2-10 parts of deionized water；
Wherein the resin binder is raw lacquer or water-base resin, and the aqueous polyanion class anticorrosive additive includes polyaniline
Or polyaniline derivative, the aqueous polyanion class anticorrosive additive further includes modifying agent, and the modifying agent is lignin sulfonic acid
Sodium, phosphoric acid and ammonium persulfate.
As can be seen from the above description, the beneficial effects of the present invention are: it is aqueous poly- by being added in raw lacquer or water-base resin
The composite anticorrosion coating of phenyl amines anticorrosive additive has excellent antiseptic property, while the coating height divides admittedly and low VOC, is
A kind of environmentally protective anti-corrosion composite coating.
Further, the water-base resin include aqueous epoxy resins, it is aqueous alkide resin, aqueous polyester resin, aqueous
Phenolic resin, water-based acrylic resin, waterborne polyurethane resin, waterborne organic silicon resin, aqueous organic fluorine and aqueous ammonia
One of base resin is a variety of.
As can be seen from the above description, aqueous polyanion class anticorrosive additive can with numerous kinds of water-base resin is compound is prevented
Rotten composite coating.
Further, the polyaniline and polyaniline derivative are obtained by monomer reactant polymerization reaction, the polyphenyl
The monomer reactant of amine is aniline, and the monomer reactant of the polyaniline derivative is 4- fluoroaniline or aniline and 4- fluoroaniline
Mixture.
Further, the preparation method of above-mentioned environmental friendly, anti-corrosive composite coating, comprising the following steps:
Step 1: sodium lignin sulfonate and phosphoric acid will be stated in molar ratio be 0.1-1.5:0.1-1 and be dissolved in deionized water
To reaction solution；
Step 2: the monomer reactant being added in the reaction solution and is uniformly mixing to obtain mixed reactant, wherein institute
The molar ratio for stating monomer reactant and sodium lignin sulfonate is 0.5-3:0.5-3；
Step 3: ammonium persulfate being dissolved in deionized water to be then added in the mixed reactant and reacts 10-12h, is obtained
To reaction product, wherein the ammonium persulfate and sodium lignin sulfonate molar ratio are 0.1-1:0.2-2；
Step 4: the reaction product being added drop-wise in organic solvent and is stirred, solid sediment is precipitated, is sunk after filtering
Precipitating crude product washing is filtered and is dried in vacuo to obtain aqueous polyanion class anticorrosive additive again by shallow lake crude product；
Step 5: by the aqueous polyanion class anticorrosive additive ultrasonic disperse in deionized water, then it is multiple with resin binder
Conjunction stirs to get environmental friendly, anti-corrosive composite coating.
Further, reaction temperature is 2-5 in step 3 described in the preparation method of above-mentioned environmental friendly, anti-corrosive composite coating
℃。
Further, the organic solvent in step 4 described in the preparation method of above-mentioned environmental friendly, anti-corrosive composite coating is
One of isopropanol, acetone and ethyl alcohol are a variety of.
Further, the vacuum drying temperature in step 4 described in the preparation method of above-mentioned environmental friendly, anti-corrosive composite coating
Degree is 50-60 DEG C, and drying time is for 24 hours.
Further, the step 5 ultrasonic disperse time described in the preparation method of above-mentioned environmental friendly, anti-corrosive composite coating is
10-30min, mixing time 10-30min.
As can be seen from the above description, it is anti-that the environment-friendly type including aqueous polyanion class anticorrosive additive can be made by the above method
Rotten composite coating.
Embodiment 1:
0.1mol sodium lignin sulfonate and 0.1mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the aniline of 0.1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.05mol ammonium persulfate is dissolved
It obtains ammonium persulfate solution in deionized water to be added in mixed reactant, reaction temperature is 4 DEG C, and reaction time 10h is obtained
Reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering, it will
Precipitating crude product washing filters to be dried in vacuo again, and vacuum drying temperature is 50 DEG C, and drying time is for 24 hours, to obtain aqueous poly-
Phenyl amines anticorrosive additive, the aqueous polyanion class anticorrosive additive include the polyaniline reacted by aniline polymerization and change
Property agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 4 parts of deionized water, when ultrasonic disperse
Between be 10min, then obtain environmental friendly, anti-corrosive composite coating with 100 parts of raw lacquer composite stirring 10min.
Embodiment 2:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the aniline of 2mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is dissolved in
It obtains ammonium persulfate solution in deionized water to be added in mixed reactant, reaction temperature is 2 DEG C, reaction time 10h, is obtained anti-
Product is answered, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering, will be sunk
Crude product washing in shallow lake filters to be dried in vacuo again, and vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous polyphenyl
Amine anticorrosive additive, the aqueous polyanion class anticorrosive additive include the polyaniline reacted by aniline polymerization and modification
Agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 100 parts of raw lacquer composite stirring 25min.
Embodiment 3:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 2 DEG C, and reaction time 10h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include the polyphenyl obtained by 4- fluoroaniline polymerization reaction
Amine derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive filler in 5 parts of deionized water, ultrasound point
Dissipating the time is 25min, then obtains environmental friendly, anti-corrosive composite coating with 100 parts of raw lacquer composite stirring 25min.
Embodiment 4:
1.5mol sodium lignin sulfonate and 1mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added in reaction vessel,
The mix reagent of the aniline of 1mol and 4- fluoroaniline (molar ratio is 1:6 between the two) is added in reaction solution again and is stirred evenly
Mixed reactant is obtained, 0.75mol ammonium persulfate is dissolved in deionized water and obtains ammonium persulfate solution to be added to mixing anti-
It answers in object, reaction temperature is 5 DEG C, and reaction time 11h obtains reaction product, then reaction product is added drop-wise in acetone and is stirred, analysis
Solid sediment out obtains precipitating crude product after filtering, precipitating crude product washing is filtered and is dried in vacuo again, is dried in vacuo
Temperature is 60 DEG C, and drying time is for 24 hours, to obtain aqueous polyanion class anticorrosive additive, the aqueous polyanion class anti-corrosion addition
Agent includes the polyaniline derivative and modifying agent sodium lignin sulfonate, phosphorus obtained by aniline and 4- fluorobenzene amine blends polymerization reaction
Acid and ammonium persulfate.
Take above-mentioned 15 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 2 parts of deionized water, when ultrasonic disperse
Between be 30min, then obtain environmental friendly, anti-corrosive composite coating with 150 parts of raw lacquer composite stirring 30min.
Embodiment 5:
1.0mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the mix reagent of the aniline of 1mol and 4- fluoroaniline (molar ratio is 3:7 between the two) is added in reaction solution and is stirred
Mixed reactant uniformly is obtained, 0.5mol ammonium persulfate is dissolved in deionized water and obtains ammonium persulfate solution and is added to mixing
In reactant, reaction temperature is 2 DEG C, and reaction time 10h obtains reaction product, then reaction product is added drop-wise in acetone and is stirred,
Solid sediment is precipitated, precipitating crude product is obtained after filtering, precipitating crude product washing is filtered and is dried in vacuo again, vacuum is dry
Dry temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous polyanion class anticorrosive additive, the aqueous polyanion class anti-corrosion adds
Add agent include the polyaniline derivative obtained by aniline and 4- fluorobenzene amine blends polymerization reaction and modifying agent sodium lignin sulfonate,
Phosphoric acid and ammonium persulfate.
Take above-mentioned 12 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 100 parts of raw lacquer composite stirring 25min.
Embodiment 6:
2mol sodium lignin sulfonate and 0.5mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added in reaction vessel,
The mix reagent of the aniline of 1mol and 4- fluoroaniline (molar ratio is 3:5 between the two) is added in reaction solution again and is stirred evenly
Mixed reactant is obtained, 0.5mol ammonium persulfate is dissolved in deionized water and obtains ammonium persulfate solution and is added to hybrid reaction
In object, reaction temperature is 2 DEG C, and reaction time 10h obtains reaction product, then reaction product is added drop-wise in acetone and is stirred, and is precipitated
Solid sediment obtains precipitating crude product after filtering, precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature
Degree is 50 DEG C, and drying time is for 24 hours, to obtain aqueous polyanion class anticorrosive additive, the aqueous polyanion class anticorrosive additive
Including the polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid obtained by aniline and 4- fluorobenzene amine blends polymerization reaction
And ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 10 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 100 parts of raw lacquer composite stirring 25min.
Embodiment 7:
1.0mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the mix reagent of the aniline of 1mol and 4- fluoroaniline (molar ratio is 5:5 between the two) is added in reaction solution and is stirred
Mixed reactant uniformly is obtained, 0.5mol ammonium persulfate is dissolved in deionized water and obtains ammonium persulfate solution and is added to mixing
In reactant, reaction temperature is 2 DEG C, and reaction time 10h obtains reaction product, then reaction product is added drop-wise in acetone and is stirred,
Solid sediment is precipitated, precipitating crude product is obtained after filtering, precipitating crude product washing is filtered and is dried in vacuo again, vacuum is dry
Dry temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous polyanion class anticorrosive additive, the aqueous polyanion class anti-corrosion adds
Add agent include the polyaniline derivative obtained by aniline and 4- fluorobenzene amine blends polymerization reaction and modifying agent sodium lignin sulfonate,
Phosphoric acid and ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 100 parts of raw lacquer composite stirring 25min.
Embodiment 8:
1.0mol sodium lignin sulfonate and 2.5mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the mix reagent of the aniline of 1mol and 4- fluoroaniline (molar ratio is 7:3 between the two) is added in reaction solution and is stirred
Mixed reactant uniformly is obtained, 0.5mol ammonium persulfate is dissolved in deionized water and obtains ammonium persulfate solution and is added to mixing
In reactant, reaction temperature is 2 DEG C, and reaction time 10h obtains reaction product, then reaction product is added drop-wise in acetone and is stirred,
Solid sediment is precipitated, precipitating crude product is obtained after filtering, precipitating crude product washing is filtered and is dried in vacuo again, vacuum is dry
Dry temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous polyanion class anticorrosive additive, the aqueous polyanion class anti-corrosion adds
Add agent include the polyaniline derivative obtained by aniline and 4- fluorobenzene amine blends polymerization reaction and modifying agent sodium lignin sulfonate,
Phosphoric acid and ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 100 parts of raw lacquer composite stirring 25min.
Embodiment 9:
1.5mol sodium lignin sulfonate and 1mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added in reaction vessel,
The mix reagent of the aniline of 1mol and 4- fluoroaniline (molar ratio is 4:1 between the two) is added in reaction solution again and is stirred evenly
Mixed reactant is obtained, 0.5mol ammonium persulfate is dissolved in deionized water and obtains ammonium persulfate solution and is added to hybrid reaction
In object, reaction temperature is 2 DEG C, and reaction time 12h obtains reaction product, then reaction product is added drop-wise in acetone and is stirred, and is precipitated
Solid sediment obtains precipitating crude product after filtering, precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature
Degree is 55 DEG C, and drying time is for 24 hours, to obtain aqueous polyanion class anticorrosive additive, the aqueous polyanion class anticorrosive additive
Including the polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid obtained by aniline and 4- fluorobenzene amine blends polymerization reaction
And ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 8 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 120 parts of raw lacquer composite stirring 25min.
Embodiment 10:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the aniline of 2mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is dissolved in
It obtains ammonium persulfate solution in deionized water to be added in mixed reactant, reaction temperature is 2 DEG C, reaction time 10h, is obtained anti-
Product is answered, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering, will be sunk
Crude product washing in shallow lake filters to be dried in vacuo again, and vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous polyphenyl
Amine anticorrosive additive, the aqueous polyanion class anticorrosive additive include reacting poly- by aniline monomer polymerization ofathe reactants
Aniline and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of property phenyl amines filler in 5 parts of deionized water, the ultrasonic disperse time is 25min,
The raw lacquer composite stirring 25min with 100 parts obtains environmental friendly, anti-corrosive composite coating again.
Embodiment 11:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 2 DEG C, and reaction time 10h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 100 parts of water-based acrylic resin composite stirring 25min.
Embodiment 12:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 2 DEG C, and reaction time 10h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 13 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 6 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 130 parts of resol resins composite stirring 25min.
Embodiment 13:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 2 DEG C, and reaction time 10h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 10 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 2 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 100 parts of aqueous alkide resin composite stirring 25min.
Embodiment 14:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 2 DEG C, and reaction time 10h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 15 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 10 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 150 parts of waterborne organic silicon resin compounded stirring 25min.
Embodiment 15:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 3 DEG C, and reaction time 11h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 12 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 120 parts of water-compatible amino resin composite stirring 25min.
Embodiment 16:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 5 DEG C, and reaction time 11h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 55 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 12 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 120 parts of waterborne polyurethane resin composite stirring 25min.
Embodiment 17:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 2 DEG C, and reaction time 12h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 50 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 12 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 120 parts of water-base epoxy ester resin compounded stirring 25min.
Embodiment 18:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 3 DEG C, and reaction time 10h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 50 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 12 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 120 parts of aqueous polyester resin composite stirring 25min.
Embodiment 19:
0.5mol sodium lignin sulfonate and 0.25mol phosphoric acid are dissolved in ionized water and obtains reaction solution and is added to reaction vessel
In, then the 4- fluoroaniline of 1mol is added in reaction solution and is uniformly mixing to obtain mixed reactant, 0.25mol ammonium persulfate is molten
Solution obtains ammonium persulfate solution in deionized water and is added in mixed reactant, and reaction temperature is 4 DEG C, and reaction time 10h is obtained
To reaction product, then reaction product is added drop-wise in acetone and is stirred, solid sediment is precipitated, precipitating crude product is obtained after filtering,
Precipitating crude product washing is filtered and is dried in vacuo again, vacuum drying temperature is 60 DEG C, and drying time is for 24 hours, to obtain aqueous
Polyaniline compound anticorrosive additive, the aqueous polyanion class anticorrosive additive include by 4- fluoroaniline monomer reactant polymerization reaction
Obtained polyaniline derivative and modifying agent sodium lignin sulfonate, phosphoric acid and ammonium persulfate.
Take above-mentioned 12 parts of ultrasonic disperses of aqueous polyanion class anticorrosive additive in 5 parts of deionized water, when ultrasonic disperse
Between be 25min, then obtain environmental friendly, anti-corrosive composite coating with 120 parts of aqueous organic fluorine composite stirring 25min.
Experiment test:
Environmental friendly, anti-corrosive composite coating made from above-described embodiment 2,3,5,7,8 and 10 is taken to be applied in advance with sand paper burnishing part
Reason, and on the black sheet iron of alcohol swab wiped clean, it is respectively labeled as LS-PANI, LS-FANI, PF-37, PF-55, PF-
73, PANI is put into climatic chamber (T=25 DEG C, RH=85%) and test sample plate is made.
Control experiment 1: take the black sheet iron for pre-processing uncoated coating labeled as substrate.
Control experiment 2: pretreated black sheet iron coating is taken to be without the raw lacquer coating for adulterating any anticorrosive packing
Blank group experiment, test sample plate obtained are simultaneously designated as L.
The test sample plate and control experiment of environmental friendly, anti-corrosive composite coating made from Example 2,3,5,7,8 and 10
Group carries out electrochemical corrosion performance test experiments by step known in this field, tests using calomel electrode as reference electrode, platinum electricity
Extremely auxiliary electrode, test sample plate are three electrode test environment of working electrode, and test solution is respectively 3.5wt%NaCl solution
With 1M HCl solution, the template of test sample plate and control experiment is put into after impregnating half an hour in test solution and starts to test
Tafel curve.Its resistance (Rp), corrosion rate (CR) and protection efficiency (PE) calculation formula are as follows:
Wherein, baAnd bcFor cathode and anode flowpath slope, IcorrFor corrosion current, D is density, and V is chemical valence.
Icorr,bareAnd Icorr,coatedIt respectively represents the current density of substrate raw lacquer and applies the current density of template after coating.
Test result is as shown in table 1, and table 1 is that the japanning sample of embodiment 2,3,5,7,8 and 10 and control experiment group exist
Electrochemical corrosion performance test result in 3.5wt%NaCl solution:
Table 1
Wherein PE (0) the columns value calculates gained by reference value of substrate, and PE (1) the columns value is using template L as reference value
Calculate gained.
Table 2 is for the test sample plate of environmental friendly, anti-corrosive composite coating made from embodiment 2,3,5,7,8 and 10 and to according to the facts
Test electrochemical corrosion performance test result of the group in 1M HCl solution:
Table 2
Wherein PE (0) the columns value calculates gained by reference value of substrate, and PE (1) the columns value is using template L as reference value
Calculate gained.
Have from the composite anticorrosion coating for adulterating filler known to above-mentioned experiment test according to prepared by embodiment excellent
Antiseptic property, the protection efficiency in 3.5wt%NaCl solution and 1M HCl etchant solution are significantly improved.
In conclusion a kind of environmental friendly, anti-corrosive composite coating provided by the invention in raw lacquer or water-base resin by adding
The composite anticorrosion coating of aqueous polyanion class anticorrosive additive has excellent antiseptic property, while the coating height divides and low admittedly
VOC is a kind of environmentally protective anti-corrosion composite coating.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (8)
1. a kind of environmental friendly, anti-corrosive composite coating, which is characterized in that meter includes following components by weight:
100-150 parts of resin binder, 10-15 parts of aqueous polyanion class anticorrosive additive, 2-10 parts of deionized water；
Wherein the resin binder is raw lacquer or water-base resin, and the aqueous polyanion class anticorrosive additive includes polyaniline or gathers
Anil, the aqueous polyanion class anticorrosive additive further includes modifying agent, and the modifying agent is sodium lignin sulfonate, phosphorus
Acid and ammonium persulfate.
2. environmental friendly, anti-corrosive composite coating according to claim 1, which is characterized in that the water-base resin includes aqueous ring
Oxygen resin, aqueous alkide resin, aqueous polyester resin, resol resins, water-based acrylic resin, waterborne polyurethane resin,
One of waterborne organic silicon resin, aqueous organic fluorine and water-compatible amino resin are a variety of.
3. environmental friendly, anti-corrosive composite coating according to claim 1, which is characterized in that the polyaniline and polyaniline are derivative
Object is obtained by monomer reactant polymerization reaction, and the monomer reactant of the polyaniline is aniline, the polyaniline derivative
Monomer reactant is the mixture of 4- fluoroaniline or aniline and 4- fluoroaniline.
4. the preparation method of environmental friendly, anti-corrosive composite coating according to claim 1-3, which is characterized in that including
Following steps:
Step 1: sodium lignin sulfonate and phosphoric acid will be stated in molar ratio be 0.1-1.5:0.1-1 be dissolved in deionized water obtain it is anti-
Answer liquid；
Step 2: the monomer reactant being added in the reaction solution and is uniformly mixing to obtain mixed reactant, wherein the list
The molar ratio of precursor reactant object and sodium lignin sulfonate is 0.5-3:0.5-3；
Step 3: ammonium persulfate being dissolved in deionized water to be then added in the mixed reactant and reacts 10-12h, is obtained anti-
Product is answered, wherein the ammonium persulfate and sodium lignin sulfonate molar ratio are 0.1-1:0.2-2
Step 4: the reaction product being added drop-wise in organic solvent and is stirred, solid sediment is precipitated, it is thick that precipitating is obtained after filtering
Precipitating crude product washing is filtered and is dried in vacuo to obtain aqueous polyanion class anticorrosive additive again by product；
Step 5: by the aqueous polyanion class anticorrosive additive ultrasonic disperse in deionized water, then with resin binder is compound stirs
It mixes to obtain environmental friendly, anti-corrosive composite coating.
5. the preparation method of environmental friendly, anti-corrosive composite coating according to claim 4, which is characterized in that in the step 3
Reaction temperature is 2-5 DEG C.
6. the preparation method of environmental friendly, anti-corrosive composite coating according to claim 4, which is characterized in that in the step 4
Organic solvent be one of isopropanol, acetone and ethyl alcohol or a variety of.
7. the preparation method of environmental friendly, anti-corrosive composite coating according to claim 4, which is characterized in that in the step 4
Vacuum drying temperature be 50-60 DEG C, drying time be for 24 hours.
8. the preparation method of environmental friendly, anti-corrosive composite coating according to claim 4, which is characterized in that the step 5 surpasses
Sound jitter time is 10-30min, mixing time 10-30min.
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| CN113897111A (en) * | 2021-11-09 | 2022-01-07 | 重庆三峡油漆股份有限公司 | Workshop primer and preparation method and preparation system thereof |
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| CN114634748A (en) * | 2022-04-16 | 2022-06-17 | 四川海纳泓洁科技有限公司 | Preparation method of flame-retardant polyaniline composite water-based anticorrosive paint |
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