CN116925349B - Chemically modified polyaniline composite anticorrosive paint and preparation method thereof - Google Patents
Chemically modified polyaniline composite anticorrosive paint and preparation method thereofInfo
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- CN116925349B CN116925349B CN202310906828.2A CN202310906828A CN116925349B CN 116925349 B CN116925349 B CN 116925349B CN 202310906828 A CN202310906828 A CN 202310906828A CN 116925349 B CN116925349 B CN 116925349B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
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- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/18—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
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- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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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- 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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Abstract
The invention relates to a chemical modified polyaniline composite anti-corrosion coating and a preparation method thereof, and relates to the technical field of corrosion prevention. The anticorrosive paint is prepared by dispersing modified polyaniline in epoxy resin in the presence of an epoxy curing agent, wherein modified polyaniline is obtained by polymerizing modified aniline monomers, and the modified polyaniline monomers are obtained by Michael addition reaction of specific long-chain modifiers and aniline monomers. The chemically modified polyaniline composite anticorrosive paint provided by the invention can realize long-time anticorrosive performance of metal materials, shows stable corrosion resistance in a neutral salt spray environment, is simple in preparation process, low in cost, does not contain toxic substances, and is suitable for wide popularization.
Description
Technical Field
The invention relates to the technical field of corrosion prevention, in particular to a chemical modified polyaniline composite corrosion-resistant coating and a preparation method thereof.
Background
The corrosion of metal materials consumes a large amount of resources, causes great economic loss, and simultaneously easily causes disastrous accidents, thereby causing a series of natural environmental pollution. Therefore, the method has very important practical significance in improving the corrosion resistance of metal and reducing various losses caused by corrosion of metal materials.
The most common method for solving the corrosion problem of metal materials at present is to carry out metal surface treatment, and especially the preparation of anti-corrosion paint is particularly important. Polyaniline can interact with metals through oxidation-reduction state and doping-dedoping state transition, and the effect can enable corrosion potential of metal substrates to be positively moved so as to enable the metals to be in passivation state. Therefore, polyaniline has been expected to find wide application as a novel green preservative material.
However, polyaniline has the disadvantages of strong skeleton rigidity of molecular chains, difficult processing and forming, poor adhesion of pure polyaniline and a metal substrate, low utilization rate and the like, and limits practical application. Therefore, polyaniline needs to be modified, so that the problems of dispersibility of polyaniline in the coating and mechanical properties of the coating are solved, and the corrosion resistance of the modified polyaniline coating is further improved.
Disclosure of Invention
The invention aims to provide a chemical modified polyaniline composite anticorrosive paint and a preparation method thereof, which are used for solving the problems in the prior art. The invention realizes the high hydrophobic property of polyaniline material by chemical bond doping modification mode, and based on the modified polyaniline structure design of the invention, the preparation scheme of the composite anticorrosive paint can avoid the property of polyaniline in resin being changed due to the doping modification of the chemical bond of polyaniline, thereby influencing the anticorrosive property of the paint. The composite anticorrosive paint prepared by the invention has higher electrochemical impedance modulus, is stable in neutral salt fog for a long time, and has good anticorrosive performance.
In order to achieve the above object, the present invention provides the following solutions:
the technical scheme of the invention provides chemical modified polyaniline, which is obtained by polymerizing modified aniline monomers, wherein the modified aniline monomers are obtained by Michael addition reaction of long-chain modifiers and aniline monomers;
The long-chain modifier is perfluoroalkyl methacrylate, butyl acrylate or gamma-methacryloxypropyl trimethoxy silane.
The second technical scheme of the invention provides application of the chemical modified polyaniline in anticorrosive paint.
The third technical proposal of the invention is to provide a chemical modified polyaniline composite anticorrosive paint which is obtained by dispersing modified polyaniline in epoxy resin in the presence of an epoxy curing agent;
The modified polyaniline is polymerized by modified aniline monomers;
The modified aniline monomer is obtained through Michael addition reaction of a long-chain modifier and an aniline monomer;
The long-chain modifier is one of perfluoroalkyl methacrylate, butyl acrylate and gamma-methacryloxypropyl trimethoxy silane.
Further, the epoxy resin is E44 epoxy resin, and the epoxy curing agent is polyamide resin.
Further, the dispersion system also contains a solvent and an auxiliary agent, wherein the auxiliary agent comprises a leveling agent and a defoaming agent. Preferably, the leveling agent is the humus 435 with the addition amount of 0.2% of the dispersion system, and the defoamer is the humus 5500 with the addition amount of 0.2% of the dispersion system.
Further, the solvent is diphenylamine.
The invention can realize that the contact angle of the modified polyaniline is larger than 150 degrees, the chemically modified polyaniline is uniformly dispersed in the epoxy resin, and the obtained chemically modified polyaniline composite anticorrosive paint has excellent anticorrosive performance on the surfaces of metals such as low-carbon steel and the like.
The fourth technical scheme of the invention is to provide a preparation method of the chemical modified polyaniline composite anticorrosive paint, which comprises the following steps:
Firstly, carrying out Michael addition reaction on an aniline monomer by using a long-chain modifier to obtain a modified aniline monomer, then polymerizing the modified aniline monomer to obtain modified polyaniline, and finally dispersing the modified polyaniline in epoxy resin in the presence of an epoxy curing agent to obtain the chemically modified polyaniline composite anticorrosive paint.
Further, the molar ratio of the aniline monomer to the long-chain modifier is 5:1-1:1, and the mass ratio of the modified polyaniline to the epoxy curing agent to the epoxy resin is (2 g-50 g) 100g to 100g.
Further, the invention adopts a chemical oxidation method to prepare the modified polyaniline, namely the polymerization mode adopts oxidation polymerization.
Further, the oxidant used in the oxidative polymerization is ammonium persulfate.
In the invention, after the chemical oxidation is completed, the method further comprises the steps of centrifugation, washing and drying.
Preferably, the washing is carried out by using a mixture of ethanol and water (volume ratio is 1:1), the drying is carried out by vacuum drying, the drying temperature is 60 ℃, and the drying time is 24 hours.
Further, the catalyst used in the Michael addition is trifluoroacetic acid, the preferable addition amount is 0.2% of the sum of the mass of the long-chain modifier and the mass of the aniline monomer, and the Michael addition reaction time is 6 hours.
Further, the time of the oxidative polymerization is 24 hours, and the molar ratio of the aniline monomer to the ammonium persulfate is 1:1. Preferably, an aqueous ammonium persulfate solution is used, and the concentration of the solution is preferably 0.1mol/L.
Further, in the preparation of the present invention, the solvent and the auxiliary agent are added to the dispersion, and the addition is performed in the above-described preferred manner.
The fifth technical scheme of the invention provides application of the chemical modified polyaniline composite anticorrosive paint in the field of metal corrosion prevention. Preferably low carbon steel.
The chemical modified polyaniline obtained by the invention is greatly different from the traditional doped polyaniline in structure, the traditional doped polyaniline is prepared by doping hydrophobic ions when an aniline monomer is oxidized to obtain hydrophobic or super-hydrophobic polyaniline, the hydrophobic dopant is connected with the polyaniline through physical action, and the hydrophobic dopant is slowly undoped from polyaniline particles in a long-term aqueous environment so as to lose super-hydrophobic performance, and the chemical modified polyaniline is oxidized into the modified polyaniline (taking PFMA modified polyaniline as an example, a reaction equation is shown below) after the chemical modified polyaniline is modified by Michael addition reaction to obtain the chemical modified polyaniline, wherein the hydrophobic dopant is not undoped with the extension of service time, so that the protective performance of a coating is prolonged.
The invention discloses the following technical effects:
The chemical modified polyaniline has superhydrophobicity, can realize that the contact angle is larger than 150 degrees, still has good hydrophobic property after being compounded with epoxy resin, and can realize synergistic corrosion prevention with compact isolation property of the epoxy resin and passivation effect of polyaniline, so that the chemical modified polyaniline composite anticorrosive paint can realize long-time corrosion prevention property, and the metal material can show stable corrosion resistance in a neutral salt fog environment.
The chemically modified polyaniline composite anticorrosive paint has the advantages of simple preparation process, low cost, no toxic substances and suitability for wide popularization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of PFMA modified aniline monomer prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of KH 570-modified aniline monomer prepared in example 4 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of BA modified aniline monomer prepared in example 7 of the present invention;
FIG. 4 is an infrared spectrum of polyaniline (prepared in comparative example 1), PFMA-modified polyaniline (prepared in example 1), KH 570-modified polyaniline (prepared in example 4), and BA-modified polyaniline (prepared in example 7).
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the following examples of the present invention are all commercially available. Aniline, trifluoroacetic acid, perfluoroalkyl methacrylate (PFMA), butyl Acrylate (BA), gamma-methacryloxypropyl trimethoxysilane (KH 570), ammonium persulfate from Shanghai milin Biochemical technologies, ethanol and xylene from Hangzhou high definition chemical Co., ltd, and epoxy resins and epoxy curing agents from Nantong star synthetic materials Co., ltd.
The preparation method of the chemically modified polyaniline anticorrosive paint mainly comprises the following two steps of (1) obtaining chemically modified polyaniline through a chemical oxidation method on the basis of chemically modified aniline monomers, and (2) compounding the chemically modified polyaniline with epoxy resin and other auxiliary agents to prepare the chemically modified polyaniline anticorrosive paint.
The following examples serve as further illustrations of the technical solutions of the invention.
First stage, preparation of chemically modified polyaniline
Example 1
Taking 9.3g of aniline (0.1 mol), 54.2g of PFMA (0.1 mol) and 0.127g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain PFMA modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain PFMA modified polyaniline 1-1.
The nuclear magnetic spectrum of the PFMA modified aniline monomer obtained in the embodiment is shown in fig. 1, the characteristic information of 7.17ppm of chemical shift is obviously aromatic protons, a single peak is presented, the paramagnetic shift is generated along with the increase of a conjugated system, a deshielding effect is generated, the impurity peak around 7.17ppm is a residual peak of a solvent, the chemical shift is 7.28ppm and belongs to an N-H bond, and multiple peaks appear between the chemical shift and 7.17-7.28 ppm, which indicates that a doping reaction occurs, and the success of the preparation of the grafted modified aniline monomer is indicated.
The infrared spectrum of the PFMA modified polyaniline (namely PFMA modified polyaniline 1-1) obtained in this example is shown in FIG. 4. It can be seen that the peak at 3459cm -1 is relatively broad, belonging to the stretching vibration of N-H bonds, the peaks at 2722 and 2823cm -1 are stretching vibration of C-H bonds on aromatic rings, the peak at 1601cm -1 is quinoid structure C=C bond stretching, the peak at 1380cm -1 is C-H deformation vibration absorption peak, the peak at 1354cm -1 corresponds to C-F bond stretching, the peak at 1750-160 cm -1 is significantly broadened compared with polyaniline, mainly caused by overlapping of stretching vibration peak of C=O bonds in PFMA and stretching peak of quinoid structure C=C bond, and the peak at 775cm -1 is disubstituted C-H bond out-of-plane bending vibration on benzene ring.
The PFMA modified polyaniline 1-1 obtained in this example is black rod-like powder of about 1 micron in length and 100nm in diameter, and the static water contact angle of the pressed sheet is 162 °.
Example 2
Taking 9.3g of aniline (0.1 mol), 18.1g of PFMA (0.03 mol) and 0.047g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain PFMA modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain PFMA modified polyaniline 3-1.
The PFMA modified polyaniline 3-1 obtained in this example is black rod-like powder of about 1 micron in length and 100nm in diameter, and the static water contact angle of the pressed sheet is 158 °.
Example 3
Taking 9.3g of aniline (0.1 mol), 10.8g of PFMA (0.02 mol) and 0.040g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain PFMA modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain PFMA modified polyaniline 5-1.
The PFMA modified polyaniline 5-1 obtained in this example is a black rod-like powder of about 1.5 μm in length and 80 nm in diameter, and the static water contact angle of the pressed sheet is 155 °.
Example 4
Taking 9.3g of aniline (0.1 mol), 24.8g of KH570 (0.1 mol) and 0.068g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain KH570 modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain KH570 modified polyaniline 1-1.
The nuclear magnetic spectrum of the KH570 modified aniline monomer obtained in the embodiment is shown in fig. 2, and it can be seen from fig. 2 that chemical shift is 7.14ppm and belongs to N-H bond, chemical shift is 3.41-3.57 and belongs to C-H bond on branched chain, chemical shift is 4.08ppm and belongs to H atom of sp 2 hybridization to generate de-shielding effect, chemical shift is 6.63-7.14 ppm and is C-H bond on benzene ring, multiple peaks appear, which indicates that KH570 successfully reacts with aniline monomer.
The infrared spectrum of KH 570-modified polyaniline 1-1 obtained in this example is shown in FIG. 4. It can be seen that the peak at 3459cm -1 is wider, belonging to the stretching vibration of N-H bond, the peaks at 2722 and 2823cm -1 are the stretching vibration of C-H bond on aromatic ring, the peak at 1601cm -1 is the stretching of C=C bond of quinone structure, the peak at 1380cm -1 is the absorption peak of C-H deformation vibration, the peak at 775cm -1 is the bending vibration out of plane of C-H bond on disubstituted benzene ring, compared with polyaniline, the peak at 1750-160 cm -1 is obviously widened, mainly caused by the overlapping of the stretching vibration peak of C=O bond in KH570 and the stretching peak of C=C bond of quinone structure, the peak at 1089cm -1 is the antisymmetric stretching vibration of Si-O bond, which indicates that KH570 modified polyaniline is successfully prepared.
The KH 570-modified polyaniline 1-1 obtained in this example was a black rod-like powder having a length of about 2 μm and a diameter of 100 nm, and the static water contact angle of the pressed sheet was 159 °.
Example 5
Taking 9.3g of aniline (0.1 mol), 12.4g of KH570 (0.05 mol) and 0.043g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain KH570 modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain KH570 modified polyaniline 2-1. The PFMA modified polyaniline 2-1 obtained in this example is black rod-like powder of about 2 microns in length and 90 nm in diameter, and the static water contact angle of the pressed sheet is 154 °.
Example 6
Taking 9.3g of aniline (0.1 mol), 4.7g of KH570 (0.02 mol) and 0.028g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain KH570 modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain KH570 modified polyaniline 5-1. The PFMA modified polyaniline 5-1 obtained in this example is black rod-like powder of about 2 microns in length and 100 nm in diameter, and the static water contact angle of the pressed sheet is 152 °.
Example 7
Taking 9.3g of aniline (0.1 mol), 12.8g of BA (0.1 mol) and 0.044g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain BA modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain BA modified polyaniline 1-1.
The nuclear magnetic spectrum of the BA modified aniline monomer obtained in the embodiment is shown in fig. 3, and as can be seen from fig. 3, the chemical shift is 6.68-7.18 ppm and belongs to-CH bond on benzene ring, and multiple peaks appear, which also indicate that BA successfully reacts with aniline monomer, electrons can generate transition to generate vibration due to doping state, shielding effect is reduced, the chemical shift is 5.81ppm and belongs to N-H bond, and the chemical shift is 0.94-1.69 and belongs to branched C-H bond.
The infrared spectrum of the BA-modified polyaniline 1-1 obtained in the embodiment is shown in fig. 4, and it can be seen from fig. 4 that the peak at 3459cm -1 is wider, the peak at 2722 and 2823cm -1 is the stretching vibration of C-H bond on aromatic ring, the peak at 1601cm -1 is the stretching of C=C bond with quinone structure, the peak at 1380cm -1 is the absorption peak of C-H deformation vibration, the peak at 775cm -1 is the out-of-plane bending vibration of C-H bond on disubstituted benzene ring, compared with polyaniline, the peak at 1750-1600cm -1 is obviously widened, which is mainly caused by the overlapping of the stretching peak of C=O bond and C=C bond with the stretching peak of quinone structure in BA, and the peaks at 2960cm -1 and 2930cm -1 are the stretching vibration peaks of CH 3 and CH 2, thus indicating that the BA-modified polyaniline is successfully prepared.
The BA-modified polyaniline 1-1 obtained in this example was a black rod-like powder having a length of about 2 μm and a diameter of 150 nm, and the static water contact angle of the pressed sheet was 155 °.
Example 8
Taking 9.3g of aniline (0.1 mol), 6.2g of BA (0.05 mol) and 0.043g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain BA modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain BA modified polyaniline 2-1. The BA-modified polyaniline 2-1 obtained in this example was a black rod-like powder having a length of about 2 μm and a diameter of 150 nm, and the static water contact angle of the pressed sheet was 153 °.
Example 9
Taking 9.3g of aniline (0.1 mol), 2.56g of BA (0.02 mol) and 0.028g of trifluoroacetic acid, fully stirring and reacting for 6 hours to obtain BA modified aniline monomer, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24 hours to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24 hours to obtain BA modified polyaniline 5-1. The BA-modified polyaniline 5-1 obtained in this example was a black rod-like powder having a length of about 2 μm and a diameter of 150 nm, and the static water contact angle of the pressed sheet was 150 °.
Comparative example 1
Taking 9.3g of aniline, adding 1000mL of 0.1mol/L ammonium persulfate solution, standing for 24h to complete oxidation reaction, centrifuging the obtained mixture, washing with 50% ethanol water solution for 3 times, and vacuum drying at 60 ℃ for 24h to obtain polyaniline.
As shown in FIG. 4, the infrared spectrum of the polyaniline obtained in the comparative example is shown in FIG. 4, wherein the peak at 3459cm -1 is wider, the peaks at 2722 and 2823cm -1 are the stretching vibration of C-H bond on aromatic ring, the peak at 1601cm -1 is the stretching of C=C bond with quinone structure, the peak at 1380cm -1 is the absorption peak of C-H deformation vibration, and the peak at 775cm -1 is the out-of-plane bending vibration of C-H bond on disubstituted benzene ring, which indicates that the polyaniline is successfully prepared.
The polyaniline obtained in this example was a black powder agglomerated with particles having a particle size of about 200nm, and the static water contact angle of the pressed sheet was 43 °.
Second stage, preparation of chemically modified polyaniline composite coating
Example 10
Uniformly mixing 2g of PFMA modified polyaniline 1-1, 100g of polyamide resin epoxy curing agent, 20g of dimethylbenzene, 0.444g of Qoqin 435 leveling agent and 0.444g of Qoqin 5500 defoaming agent, grinding for 3 times by a conical mill, and stirring 100g of E44 epoxy resin uniformly to obtain the PFMA modified polyaniline composite anti-corrosive paint 1. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 2H, the electrochemical impedance modulus value is 8.6X10 9Ωcm2, the salt fog is 600H, the color is not changed, the peeling is not generated, the falling is not caused, and the pulverization is not generated.
Example 11
Uniformly mixing 12g of PFMA modified polyaniline 1-1, 100g of polyamide resin epoxy curing agent, 25g of dimethylbenzene, 0.474g of Qoqin 435 leveling agent and 0.474g of Qoqin 5500 defoaming agent, grinding for 3 times by a conical mill, and stirring 100g of E44 epoxy resin uniformly to obtain the PFMA modified polyaniline composite anti-corrosive paint 2. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 2H, the electrochemical impedance modulus value is 9.7X10 9Ωcm2, the salt fog is 600H, the color is not changed, the skin is not peeled off, and the powder is not atomized.
Example 12
Uniformly mixing 25g of PFMA modified polyaniline 1-1, 100g of polyamide resin epoxy curing agent, 30g of dimethylbenzene, 0.51g of Qigong 435 flatting agent and 0.51g of Qigong 5500 defoamer, grinding for 3 times by a conical mill, and stirring 100g of E44 epoxy resin uniformly to obtain the PFMA modified polyaniline composite anti-corrosive paint 3. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 2H, the electrochemical impedance modulus value is 5.3 multiplied by 10 10Ωcm2, the salt fog is 720H, and the paint does not change color, peel, fall off and chalk.
Example 13
Uniformly mixing 40g of PFMA modified polyaniline 1-1, 100g of polyamide resin epoxy curing agent, 40g of dimethylbenzene, 0.56g of Qoqin 435 leveling agent and 0.56g of Qoqin 5500 defoaming agent, grinding for 3 times by a conical mill, and uniformly stirring 100g of E44 epoxy resin to obtain the PFMA modified polyaniline composite anticorrosive paint 4. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 3H, the electrochemical impedance modulus value is 5.7X10 10Ωcm2, the salt fog is 1000H, the paint does not change color, peel, fall off and chalk.
Example 14
50G of PFMA modified polyaniline 1-1, 100g of polyamide resin epoxy hardener, 50g of dimethylbenzene, 0.6g of Qoqin 435 flatting agent and 0.6g of Qoqin 5500 defoamer are uniformly mixed, and 100g of E44 epoxy resin is uniformly stirred after being ground for 3 times by a conical mill, so that the PFMA modified polyaniline composite anti-corrosive paint 5 is obtained. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 1 level, the hardness is 3H, the electrochemical impedance modulus value is 8.3 multiplied by 10 10Ωcm2, and the salt fog is not discolored, peeled, fallen and pulverized for 1200H.
Example 15
Uniformly mixing 25g of PFMA modified polyaniline 2-1, 100g of polyamide resin epoxy curing agent, 50g of dimethylbenzene, 0.55g of Qoqin 435 leveling agent and 0.55g of Qoqin 5500 defoaming agent, grinding for 3 times by a conical mill, and uniformly stirring 100g of E44 epoxy resin to obtain the PFMA modified polyaniline composite anti-corrosive paint 6. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 2H, the electrochemical impedance modulus value is 6.1 multiplied by 10 9Ωcm2, the salt fog is 720H, and the paint does not change color, peel, fall off and chalk.
Example 16
50G of PFMA modified polyaniline 5-1, 100g of polyamide resin epoxy hardener, 50g of dimethylbenzene, 0.6g of Qoqin 435 flatting agent and 0.6g of Qoqin 5500 defoamer are uniformly mixed, and after 3 times of conical grinding, 100g of E44 epoxy resin is uniformly stirred, thus obtaining the PFMA modified polyaniline composite anti-corrosive paint 7. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 1 level, the hardness is 3H, the electrochemical impedance modulus value is 5.4 multiplied by 10 9Ωcm2, the salt fog is 720H, and the paint does not change color, peel, fall off and chalk.
Example 17
Uniformly mixing 2g of KH570 modified polyaniline 1-1, 100g of polyamide resin epoxy hardener, 20g of dimethylbenzene, 0.444g of Qoqin 435 flatting agent and 0.444g of Qoqin 5500 defoamer, grinding for 3 times by a conical mill, and uniformly stirring 100g of E44 epoxy resin to obtain the KH570 modified polyaniline composite anti-corrosive paint 1. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 2H, the electrochemical impedance modulus value is 4.3 multiplied by 10 8Ωcm2, and the salt fog is 600H without color change, peeling, falling and pulverization.
Example 18
Uniformly mixing 20g KH570 modified polyaniline 1-1, 100g polyamide resin epoxy hardener, 30g dimethylbenzene, 0.5g Qoqin 435 flatting agent and 0.5g Qoqin 5500 defoamer, grinding for 3 times by a conical mill, and uniformly stirring 100g E44 epoxy resin to obtain the KH570 modified polyaniline composite anti-corrosive paint 2. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 2H, the electrochemical impedance modulus value is 9.7X10 9Ωcm2, the salt fog is 720H, the paint does not discolor, peel, fall off and chalk.
Example 19
50G of KH570 modified polyaniline 1-1, 100g of polyamide resin epoxy hardener, 50g of dimethylbenzene, 0.6g of Qoqin 435 flatting agent and 0.6g of Qoqin 5500 defoamer are uniformly mixed, and after 3 times of conical grinding, 100g of E44 epoxy resin is uniformly stirred to obtain the KH570 modified polyaniline composite anti-corrosive paint 3. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 1 level, the hardness is 2H, the electrochemical impedance modulus value is 2.3X10 10Ωcm2, the salt fog is 720H, the paint does not discolor, peel, fall off and chalk.
Example 20
Uniformly mixing 30g of KH570 modified polyaniline 3-1, 100g of polyamide resin epoxy hardener, 40g of dimethylbenzene, 0.54g of Qoqin 435 leveling agent and 0.54g of Qoqin 5500 defoamer, grinding for 3 times by a conical mill, and uniformly stirring 100g of E44 epoxy resin to obtain the KH570 modified polyaniline composite anti-corrosive paint 4. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 3H, the electrochemical impedance modulus value is 6.2 multiplied by 10 9Ωcm2, the salt fog is 600H, and the paint does not change color, peel, fall off and chalk.
Example 21
50G of KH570 modified polyaniline 1-1, 100g of polyamide resin epoxy hardener, 50g of dimethylbenzene, 0.6g of the Qoqin 435 leveling agent and 0.6g of the Qoqin 5500 defoamer are uniformly mixed, and after 3 times of conical grinding, 100g of E44 epoxy resin is uniformly stirred to obtain the KH570 modified polyaniline composite anti-corrosive paint 5. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 1 level, the hardness is 3H, the electrochemical impedance modulus value is 5.4 multiplied by 10 9Ωcm2, the salt fog is 600H, and the paint does not change color, peel, fall off and chalk.
Example 22
Uniformly mixing 2g of BA modified polyaniline 1-1, 100g of polyamide resin epoxy curing agent, 20g of dimethylbenzene, 0.444g of the Qoqin 435 leveling agent and 0.444g of the Qoqin 5500 defoaming agent, grinding for 3 times by a conical mill, and uniformly stirring 100g of E44 epoxy resin to obtain the BA modified polyaniline composite anticorrosive paint 1. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 0 level, the hardness is 2H, the electrochemical impedance modulus value is 8.4 multiplied by 10 8Ωcm2, and the salt fog is 600H without color change, peeling, falling and pulverization.
Example 23
Uniformly mixing 30g of BA modified polyaniline 1-1, 100g of polyamide resin epoxy curing agent, 30g of dimethylbenzene, 0.52g of the Qoqin 435 leveling agent and 0.52g of the Qoqin 5500 defoaming agent, grinding for 3 times by a conical mill, and uniformly stirring 100g of E44 epoxy resin to obtain the BA modified polyaniline composite anticorrosive paint 2. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 1 level, the hardness is 2H, the electrochemical impedance modulus value is 7.4 multiplied by 10 10Ωcm2, the salt fog is 720H, and the paint does not change color, peel, fall off and chalk.
Example 24
50G of BA modified polyaniline 1-1, 100g of polyamide resin epoxy hardener, 50g of dimethylbenzene, 0.6g of the Qoqin 435 leveling agent and 0.6g of the Qoqin 5500 defoamer are uniformly mixed, and 100g of E44 epoxy resin is uniformly stirred after being ground for 3 times by a conical mill, so that the BA modified polyaniline composite anticorrosive paint 3 is obtained. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 2 level, the hardness is 2H, the electrochemical impedance modulus value is 9.1 multiplied by 10 10Ωcm2, the salt fog is 1000 hours, the color is not changed, the peeling is not generated, the falling is not caused, and the pulverization is not generated.
Example 25
Uniformly mixing 25g of BA modified polyaniline 2-1, 100g of polyamide resin epoxy curing agent, 40g of dimethylbenzene, 0.53g of the Qoqin 435 leveling agent and 0.53g of the Qoqin 5500 defoaming agent, grinding for 3 times by a conical mill, and uniformly stirring 100g of E44 epoxy resin to obtain the BA modified polyaniline composite anticorrosive paint 4. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 1 level, the hardness is 2H, the electrochemical impedance modulus value is 4.7X10 9Ωcm2, the salt fog is 600H, the color is not changed, the skin is not peeled off, and the powder is not atomized.
Example 26
50G of BA modified polyaniline 5-1, 100g of polyamide resin epoxy hardener, 50g of dimethylbenzene, 0.6g of the Qoqin 435 leveling agent and 0.6g of the Qoqin 5500 defoamer are uniformly mixed, and 100g of E44 epoxy resin is uniformly stirred after being ground for 3 times by a conical mill, so that the BA modified polyaniline composite anticorrosive paint 5 is obtained. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 2 level, the hardness is 2H, the electrochemical impedance modulus value is 2.4X10 9Ωcm2, the salt fog is 600H, the color is not changed, the skin is not peeled off, and the powder is not atomized.
Comparative example 2
Uniformly mixing 20g of polyaniline (prepared in comparative example 1), 100g of polyamide resin epoxy curing agent, 30g of dimethylbenzene, 0.5g of the pretty 435 leveling agent and 0.5g of the pretty 5500 defoamer, grinding for 3 times by a conical mill, and uniformly stirring 100g of E44 epoxy resin to obtain the polyaniline composite anticorrosive paint 1. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 2 level, the hardness is 2H, the electrochemical impedance modulus value is 5.3 multiplied by 10 7Ωcm2, the salt fog is 600H, and the paint does not change color, peel, fall off and chalk.
Comparative example 3
50G of polyaniline (prepared in comparative example 1), 100g of polyamide resin epoxy hardener, 50g of dimethylbenzene, 0.6g of the pretty 435 leveling agent and 0.6g of the pretty 5500 defoamer are uniformly mixed, and 100g of E44 epoxy resin is uniformly stirred after being ground for 3 times by a conical mill, so as to obtain the polyaniline composite anticorrosive paint 1. The obtained paint is sprayed on the surface of low carbon steel, and the performance of the paint is tested, wherein the adhesive force is 2 level, the hardness is 2H, the electrochemical impedance modulus value is 4.9X10 8Ωcm2, and the salt fog is 600H without color change, peeling, falling and pulverization.
Compared with the chemically modified polyaniline composite anticorrosive paint prepared by compounding epoxy resin, the chemically modified polyaniline prepared by the invention has more excellent anticorrosive performance than epoxy resin and conventional polyaniline/epoxy resin composite paint
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The chemically modified polyaniline is characterized in that the modified polyaniline is obtained by polymerizing a modified aniline monomer, wherein the modified aniline monomer is obtained by Michael addition reaction of a long-chain modifier and an aniline monomer;
The long-chain modifier is perfluoroalkyl methacrylate, butyl acrylate or gamma-methacryloxypropyl trimethoxy silane;
the molar ratio of the aniline monomer to the long-chain modifier is 5:1-1:1.
2. Use of a chemically modified polyaniline according to claim 1 in an anticorrosive coating.
3. A chemical modified polyaniline composite anticorrosive paint is characterized in that modified polyaniline is dispersed in epoxy resin in the presence of an epoxy curing agent;
Wherein, the
The modified polyaniline is polymerized by modified aniline monomers;
The modified aniline monomer is obtained through Michael addition reaction of a long-chain modifier and an aniline monomer;
The long-chain modifier is perfluoroalkyl methacrylate, butyl acrylate or gamma-methacryloxypropyl trimethoxy silane;
the molar ratio of the aniline monomer to the long-chain modifier is 5:1-1:1.
4. The chemically modified polyaniline composite anti-corrosive paint of claim 3, wherein the epoxy resin is E44 epoxy resin and the epoxy curing agent is polyamide resin.
5. The chemically modified polyaniline composite anti-corrosive paint of claim 3, further comprising a solvent and an auxiliary agent in a dispersion system of the modified polyaniline in the epoxy resin, wherein the auxiliary agent comprises a leveling agent and a defoaming agent.
6. The method for preparing the chemically modified polyaniline composite anti-corrosive paint according to any one of claims 3 to 5, comprising the steps of:
Firstly, carrying out Michael addition reaction on an aniline monomer by using a long-chain modifier to obtain a modified aniline monomer, then polymerizing the modified aniline monomer to obtain modified polyaniline, and finally dispersing the modified polyaniline in epoxy resin in the presence of an epoxy curing agent to obtain the chemically modified polyaniline composite anticorrosive paint.
7. The preparation method of the modified polyaniline according to claim 6, wherein the mass ratio of the modified polyaniline to the epoxy curing agent to the epoxy resin is (2 g-50 g) 100 g/100 g, the method for obtaining the modified polyaniline through polymerization of the modified aniline monomer further comprises the step of obtaining the modified polyaniline through oxidative polymerization of the modified aniline monomer, and the oxidant used in the oxidative polymerization is ammonium persulfate.
8. The process of claim 6, wherein the catalyst used in the Michael addition reaction is trifluoroacetic acid and the Michael addition reaction time is 6 hours.
9. The method according to claim 7, wherein the time of the oxidative polymerization is 24 hours, and the molar ratio of the aniline monomer to ammonium persulfate is 1:1.
10. The use of a chemically modified polyaniline composite anti-corrosion coating according to any one of claims 3-5 in the field of corrosion protection of metallic materials.
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