CN114874678B - Secondary repair polyaniline-based composite anticorrosive paint and preparation method and application thereof - Google Patents
Secondary repair polyaniline-based composite anticorrosive paint and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/61—Additives non-macromolecular inorganic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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Abstract
The invention discloses a secondary repair polyaniline-based composite anticorrosive paint, which comprises a first component and a second component, wherein the first component comprises the following components in percentage by mass: 30.0-80.0wt% of resin, 0.01-10.0wt% of polyaniline-based composite material, 0.01-10.0wt% of aniline monomer, 0.01-5.0wt% of titanium dioxide, 0.01-5.0wt% of benzoin and derivatives, 0.1-1.0wt% of coating auxiliary agent, and 1-20.0wt% of solvent, wherein the second component comprises: and a resin curing agent. Compared with the prior art, in the curing process of the coating of the polyaniline composite anticorrosive coating provided by the invention, the aniline monomer can permeate into the polyaniline molecular gaps to absorb light energy, so that the corrosion resistance of the original polyaniline composite coating can be obviously improved, and further the technical problem that the existing organic coating is easy to generate pores due to the molecular chain gaps of the polymer, or more corrosive medium enters the gaps between the coating and metal due to the fact that the integrity of the coating is damaged in the process can be effectively solved, so that the anticorrosive effect is poor can be solved.
Description
Technical Field
The invention relates to a secondary repair polyaniline-based composite anticorrosive paint, and a preparation method and application thereof, and belongs to the technical field of organic coatings.
Background
Corrosion is an inevitable loss phenomenon which is easy to occur and has important influence on the production life and economic life of people. Corrosion cost statistics in China in 2014 find that the total cost of corrosion accounts for about 3.34% of GDP in the current year. In international corrosion protection, application and economic action (IMPACT) research initiated by the international company NACE in 2016, the global corrosion cost is estimated to be $ 2.5 trillion, which is equivalent to 3.4% of the total global domestic production, and by using existing corrosion control practices, it is expected that corrosion costs will be reduced by 15% to 35%, i.e., $ 3750 to 8750 billions annually worldwide. Although the problem of corrosion is unavoidable, we can slow down the corrosion rate of the corrosion process, and how to make the material more corrosion resistant or non-corrosion is important to our research in order to reduce the cost of corrosion which is prohibitively high continuously.
At present, corrosion protection mainly comprises an electrochemical protection method, a coating method, a corrosive medium treatment method and a method for improving the corrosion resistance of the material, wherein the protection effect of an organic coating on metal mainly comprises shielding, slow release, protection of an anti-rust filler and cathodic protection. The long-term defect of the organic coating is that the gaps of molecular chains of the polymer can cause the coating to generate pores, or the solvent volatilizes to generate pores in the coating process, or the coating breaks the integrity of the coating in the long-term corrosion process so that more corrosive media enter the gaps between the coating and metal to become a main channel for infiltration of corrosion products such as water vapor, salt mist and the like, which is a main reason that the coating is difficult to protect a substrate for a long time.
Disclosure of Invention
Based on the above, the invention provides a secondary repair polyaniline-based composite anti-corrosion coating, and a preparation method and application thereof, so as to solve the technical problems that the existing organic coating is easy to generate pores due to the gaps of molecular chains of polymers, or more corrosive media enter the gaps between the coating and metal due to the fact that the integrity of the coating is damaged in the process, so that the anti-corrosion effect is poor.
The technical scheme of the invention is as follows: the secondary repair polyaniline-based composite anticorrosive paint comprises a first component and a second component, wherein the first component comprises the following components in percentage by mass:
30.0 to 80.0 weight percent of resin,
0.01 to 10.0 weight percent of polyaniline-based composite material,
0.01 to 10.0 weight percent of aniline monomer,
0.01 to 5.0 weight percent of titanium dioxide,
benzoin and derivative 0.01-5.0 wt%,
0.1 to 1.0 weight percent of coating auxiliary agent,
1 to 20.0wt percent of solvent,
and, the second component comprises:
and a resin curing agent.
Optionally, the mass ratio of the first component to the second component is 4:1-1:4.
Optionally, the resin is epoxy resin, acrylic resin or alkyd resin.
Optionally, the resin curing agent is a polyamide curing agent or an organic polyamine curing agent.
Optionally, the coating auxiliary comprises a diluent, an antifoaming agent and a leveling agent.
Optionally, the diluent is any one or more than two of toluene, acetone, N-butanol, ethanol and N-methyl pyrrolidone.
The invention also provides a preparation method of the secondary repair polyaniline-based composite anticorrosive paint, which comprises the following steps:
1) Dissolving polyaniline-based composite material, titanium dioxide, benzoin and derivatives in a solvent, and uniformly mixing with resin, aniline monomer and coating auxiliary agent to obtain a component I;
2) And uniformly mixing the component one and the component two to obtain the secondary repairing polyaniline-based composite anticorrosive paint.
The invention also provides an application of the secondary repair polyaniline-based composite anticorrosive paint as an anticorrosive coating.
Optionally, uniformly mixing the first component and the second component, performing film forming treatment, and curing by room-temperature illumination to obtain the coating. Specifically, the film forming method may be coating, spraying, etc., but is not limited thereto.
Optionally, the coating dries under natural or visible light.
The working mechanism of the invention is as follows: the aniline monomer is dispersed in gaps of macromolecules of the composite material, the monomer is changed from a valence state into a ground state under the action of the photoinitiator, free radicals are formed, a polymer is further formed, gaps of the macromolecules are filled, and the compact structure is favorable for reducing direct contact between water vapor and oxygen and a metal matrix. Meanwhile, polyaniline is used as a corrosion inhibitor, is reduced in the corrosion process, doped ions are dedoped, a part of anions in the corrosion environment can migrate to the surface of the protective matrix to cause pitting corrosion, and active free radicals can be combined with the dedoped anions more quickly under the action of a photoinitiator to form a doped state, so that the corrosion resistance of the coating can be improved.
The beneficial effects of the invention are as follows: compared with the prior art, in the curing process of the coating of the polyaniline composite anticorrosive coating provided by the invention, the aniline monomer can permeate into the polyaniline molecular gaps to absorb light energy, so that the corrosion resistance of the original polyaniline composite coating can be obviously improved, and further the technical problem that the existing organic coating is easy to generate pores due to the molecular chain gaps of the polymer, or more corrosive medium enters the gaps between the coating and metal due to the fact that the integrity of the coating is damaged in the process can be effectively solved, so that the anticorrosive effect is poor can be solved.
When the polyaniline-based composite coating is applied to the surfaces of substrates such as metal, the corrosion resistance, water resistance and the like of the metal can be greatly improved, and the service life of the substrates can be greatly prolonged.
Drawings
FIG. 1 is a schematic corrosion diagram of a secondary repair polyaniline-based composite anticorrosive paint of the present invention;
FIG. 2 is a scanning electron microscope of the product prepared in example 1;
fig. 3a is a digital camera picture of the comparative example sufficiently dried in darkness, and B is a digital camera picture of example 1 under illumination;
fig. 4 shows graphs A, B and C, and D shows Tafel polarization curves.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1:
step 1: the raw materials comprise the following components in parts by weight: 5g of polyaniline-based composite material, 2g of aniline monomer, 15ml of N-methyl pyrrolidone solvent, 50g of bisphenol A type epoxy resin, 0.05g of titanium dioxide, 0.05g of benzoin and derivatives, 0.02g of defoamer, 0.05g of flatting agent and 30g of T31 curing agent;
step 2: dispersing the polyaniline-based composite material in N-methylpyrrolidone, carrying out ultrasonic treatment for 30min, and then sequentially and mechanically stirring and uniformly mixing the polyaniline-based composite material with aniline monomer, titanium dioxide, benzoin and derivatives, defoamer, flatting agent and bisphenol A epoxy resin for 30min to obtain a component I;
step 3: 30g of curing agent is taken as a component two;
step 4: mixing the first component and the second component according to the mass ratio of 4:1, and stirring for 30min to obtain the polyaniline-based composite coating;
step 5: pouring the coating into a polytetrafluoroethylene mould to form a film, and fully drying under the irradiation of ultraviolet light.
Example 2:
step 1: the raw materials comprise the following components in parts by weight: 5g of polyaniline-based composite material, 5g of aniline monomer, 15ml of acetone solvent, 50g of bisphenol A type epoxy resin, 0.01g of titanium dioxide, 0.1g of benzoin and derivatives, 0.2g of defoamer, 0.5g of flatting agent and 30g of T31 curing agent;
step 2: dispersing the polyaniline-based composite material in acetone, performing ultrasonic treatment for 30min, and then mechanically stirring and uniformly mixing the polyaniline-based composite material with an aniline monomer, titanium dioxide, benzoin and derivatives, a defoaming agent, a leveling agent and bisphenol A epoxy resin for 30min to obtain a component I;
step 3: 30g of T31 hardener as component two;
step 4: mixing the first component and the second component according to the mass ratio of 4:1, and stirring for 30min to obtain the polyaniline-based composite coating;
step 5: pouring the coating into a polytetrafluoroethylene mould to form a film, and fully drying under the irradiation of ultraviolet light.
Example 3:
step 1: the raw materials comprise the following components in parts by weight: 0.1g of polyaniline-based composite material, 5g of aniline monomer, 20g of N-methyl pyrrolidone solvent, 60g of acrylic resin, 0.1g of titanium dioxide, 0.1g of benzoin and derivatives, 0.2g of defoamer, 0.5g of flatting agent and 20g of T07 curing agent;
step 2: dispersing the polyaniline-based composite material in an N-methyl pyrrolidone solvent, carrying out ultrasonic treatment for 30min, and then mechanically stirring and uniformly mixing the polyaniline-based composite material with an aniline monomer, titanium dioxide, benzoin and derivatives, a defoaming agent, a leveling agent and an olefine acid resin for 30min to obtain a component I;
step 3: 20g of T07 curing agent as component two;
step 4: mixing the first component and the second component according to the mass ratio of 2:1, and stirring for 30min to obtain the polyaniline-based composite coating with the weight percent of 0.1%;
step 5: pouring the coating into a polytetrafluoroethylene mould to form a film, and fully drying under the irradiation of ultraviolet light.
Comparative example:
step 1: the raw materials comprise the following components in parts by mass: 5g of polyaniline-based composite material, 2g of aniline, 15ml of N-methylpyrrolidone solvent, 50g of bisphenol A type epoxy resin, 0.05g of titanium dioxide, 0.05g of benzoin and derivatives, 0.02g of defoamer and 0.05g of flatting agent;
step 2: dispersing the polyaniline-based composite material in N-methyl pyrrolidone, carrying out ultrasonic treatment for 30min, and then mechanically stirring and uniformly mixing the polyaniline-based composite material with aniline, titanium dioxide, benzoin and derivatives, a defoaming agent, a leveling agent and resin for 30min to obtain a component I;
step 3: taking 30g of T31 curing agent as a second component;
step 4: mixing the first component and the second component according to the mass ratio of 4:1, and stirring for 30min to obtain the polyaniline-based composite coating;
step 5: pouring the paint into a polytetrafluoroethylene mould to form a film, and fully drying in a dark condition through ventilation.
The polyaniline-based composite material used in the embodiment and the comparative example is a composite material obtained by taking Graphene Oxide (GO) and aniline (An) as main raw materials and adopting a chemical oxidation polymerization method. The preparation method comprises the following steps: using Graphene Oxide (GO) dispersion as raw material, dissolving 1g pre-distilled aniline (An) as monomer in 100ml1M H 2 SO 4 In an acid solution, 3.05g of Ammonium Persulfate (APS) is taken as an oxidant, an in-situ chemical oxidation polymerization method is adopted, the reaction is continued for 12 hours in an ice bath, aniline monomers are polymerized on the surface of modified graphene oxide, absolute ethyl alcohol and deionized water are used for washing and suction filtration, and a vacuum drying is carried out at 60 ℃ for 24 hours, so that a greenish black product is obtained, and the polyaniline-based composite material is obtained. The Graphene Oxide (GO) dispersion liquid is prepared by using a Hummer method, and the specific preparation method comprises the steps of dispersing 1g of natural crystalline flake graphite in 25ml of concentrated sulfuric acid, slowly adding 3g of potassium permanganate after uniform dispersion, carrying out ice bath for 24 hours, heating to 60 ℃ for reaction for 6 hours, adding H2O2 to remove unreacted potassium permanganate, and carrying out acid washing, water washing and ultrasonic treatment to obtain the GO dispersion liquid for later use.
And (3) verification test:
1. surface image analysis
Fig. 1 is a corrosion schematic diagram of the secondary repair polyaniline-based composite anticorrosive paint of the present invention, and fig. 2 is a scanning electron microscope of the product prepared in example 1.
Fig. 3A is a photograph of a digital camera of the comparative example which is sufficiently dried in the dark, and fig. 3B is a photograph of a digital camera of example 1 which is illuminated, and it can be seen visually from the photograph that the surface of the coating layer under illumination is more glossy and the surface is also smoother.
2. Water resistance and electrochemical analysis
And (3) testing the water resistance of the adhesive film: taking the adhesive films prepared in the above examples 1 to 3 and comparative example 1, the weight is expressed as m 1 (g) Soaking the adhesive film in water for 24 hr, and recording the weight as m 2 (g) The method comprises the steps of carrying out a first treatment on the surface of the By the formula
The water absorption was calculated.
Electrochemical testing method for corrosion resistance of coating: the anticorrosive paint prepared in the above examples 1 to 3 and comparative example 1 is coated on carbon steel, a cinnabar CHI 760C type electrochemical workstation is adopted, a 3.5% NaCl aqueous solution is used as an etching medium, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, a coating sample is used as a working electrode, a scanning voltage is in a range of +/-300 mV of open circuit voltage, and a scanning speed is 5mV/s, and a polarization curve test is carried out; the frequency is 100 kHz-0.01 Hz, and the electrochemical impedance spectrum test is carried out.
Table 1 Water resistance and electrochemical test data sheet
As can be seen from table 1, the water absorption of examples 1 to 3 is significantly lower than that of comparative example 1, and the water absorption is poor, which means that the adhesive film of examples well fills the gaps of comparative example, so that the adhesive film becomes dense, water molecules are difficult to enter into the adhesive film, the protective effect on penetration of corrosive electrolyte is good, and a certain barrier effect is achieved, which is consistent with the graph A, B in fig. 3.
Fig. 4 shows graphs A, B and C, which are data graphs of ac impedance. Wherein, the graph A is plotted by the ratio of Log|Z| to Log f, and the example 1 and the comparative example are both relatively inclined straight lines, but the resistance modulus value of the example 1 at low frequency is larger. Graph B is a plot of Phase versus Log f, where the Phase angle at the highest point of example 1 is near-80 °, indicating that the example 1 organic coating corresponds to a shield with a small capacitance and a large resistance as compared to the comparative example coating, where example 1 is more resistant to penetration of the electrolyte solution into the metal substrate surface and the electrolyte solution of the comparative example is more prone to penetration into the organic layer. The graph C is a Nyquist graph, and in general, the larger the arc radius is, the larger the resistance value is, the smaller the corrosion rate is, the better the corrosion resistance of the coating is, compared with the arc radius of the capacitive reactance of the comparative coating, the arc radius of the example coating is obviously increased, which indicates that the example coating plays a role in corrosion resistance of a metal substrate, and the capacitive reactance of the example coating isThe arc radius is the largest and the corrosion resistance is the best. Figure D is a Tafel polarization plot in which the corrosion resistance of the coating is measured by the corrosion current density (I corr ) Corrosion voltage (E) corr ) Polarization resistance (Rp). In the polarization curves, the corrosion potential represents the tendency of the sample to undergo corrosion reaction, the greater the corrosion voltage is, the smaller the corrosion current density is, the lower the corrosion rate of the sample is, namely, the best corrosion resistance of the coating is obtained, the corrosion voltage and the corrosion current density of the coating can be obtained by extrapolation of the intersection points of the curves through Taphil straight line extrapolation, and specific data are shown in table 1, and the corrosion voltage in the examples has larger forward deviation than the corrosion potential in the comparative examples.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (2)
1. The preparation method of the secondary repair polyaniline-based composite anti-corrosion coating is characterized by comprising the following steps of:
step 1: the raw materials comprise the following components in parts by weight: 5g of polyaniline-based composite material, 2g of aniline monomer, 15mL of N-methyl pyrrolidone solvent, 50g of bisphenol A type epoxy resin, 0.05g of titanium dioxide, 0.05g of benzoin and derivatives, 0.02g of defoamer, 0.05g of flatting agent and 30g of T31 curing agent;
step 2: dispersing the polyaniline-based composite material in N-methylpyrrolidone, carrying out ultrasonic treatment for 30min, and then sequentially and mechanically stirring and uniformly mixing the polyaniline-based composite material with aniline monomer, titanium dioxide, benzoin and derivatives, defoamer, flatting agent and bisphenol A epoxy resin for 30min to obtain a component I;
step 3: 30g of curing agent is taken as a component two;
step 4: mixing the first component and the second component according to the mass ratio of 4:1, and stirring for 30min to obtain the polyaniline-based composite coating;
step 5: pouring the coating into a polytetrafluoroethylene mould to form a film, and fully drying by illumination under ultraviolet light;
the preparation method of the polyaniline-based composite material comprises the following steps: using graphene oxide dispersion liquid as raw material, dissolving 1g of pre-distilled aniline as monomer in 100mL of 1M H 2 SO 4 In the acid solution, 3.05g of ammonium persulfate is taken as an oxidant, an in-situ chemical oxidation polymerization method is adopted, the reaction is continued for 12 hours in an ice bath, aniline monomers are polymerized on the surface of modified graphene oxide, absolute ethyl alcohol and deionized water are used for washing and suction filtration, and vacuum drying is carried out at 60 ℃ for 24 hours, so that a greenish black product is obtained, and the polyaniline-based composite material is obtained.
2. The preparation method of the secondary repair polyaniline-based composite anti-corrosion coating is characterized by comprising the following steps of:
step 1: the raw materials comprise the following components in parts by weight: 5g of polyaniline-based composite material, 5g of aniline monomer, 15mL of acetone solvent, 50g of bisphenol A type epoxy resin, 0.01g of titanium dioxide, 0.1g of benzoin and derivatives, 0.2g of defoamer, 0.5g of flatting agent and 30g of T31 curing agent;
step 2: dispersing the polyaniline-based composite material in acetone, performing ultrasonic treatment for 30min, and then mechanically stirring and uniformly mixing the polyaniline-based composite material with an aniline monomer, titanium dioxide, benzoin and derivatives, a defoaming agent, a leveling agent and bisphenol A epoxy resin for 30min to obtain a component I;
step 3: 30g of T31 curing agent is taken as a second component;
step 4: mixing the first component and the second component according to the mass ratio of 4:1, and stirring for 30min to obtain the polyaniline-based composite coating;
step 5: pouring the coating into a polytetrafluoroethylene mould to form a film, and fully drying by illumination under ultraviolet light;
the preparation method of the polyaniline-based composite material comprises the following steps: using graphene oxide dispersion liquid as raw material, dissolving 1g of pre-distilled aniline as monomer in 100mL of 1M H 2 SO 4 In the acid solution, 3.05g of ammonium persulfateAnd (3) as an oxidant, adopting an in-situ chemical oxidation polymerization method, continuously reacting for 12 hours in an ice bath to polymerize an aniline monomer on the surface of the modified graphene oxide, washing with absolute ethyl alcohol and deionized water, filtering, and vacuum drying at 60 ℃ for 24 hours to obtain a dark green product, thereby obtaining the polyaniline-based composite material.
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