CN115216170B - Water-based epoxy resin anticorrosive paint and preparation method thereof - Google Patents
Water-based epoxy resin anticorrosive paint and preparation method 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
- 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
- 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
- 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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- C08L2312/00—Crosslinking
Abstract
The invention is thatBelongs to the technical field of anti-corrosion paint, and discloses a water-based epoxy resin anti-corrosion paint and a preparation method thereof. The invention prepares amino functional silsesquioxane through the hydrolytic condensation reaction of the silane coupling agent, and uses tannic acid as a multifunctional reaction center to prepare NH 2 Grafting of POSS to SiO 2 Surface, preparing POSS modified nano SiO 2 A hybrid material. The invention uses epoxy resin and POSS-TA-SiO 2 The water-based epoxy resin anticorrosive paint is prepared by stirring and reacting the hybrid material, the water-based curing agent, the water-based dispersing agent, the water-based leveling agent and the water-based defoaming agent. The invention uses POSS-TA-SiO 2 The hybrid material remarkably improves the crosslinking density and the surface hydrophobicity of the coating, simultaneously effectively reduces the micropore structure generated by curing of the coating, delays the time of corrosive medium in the environment reaching the metal substrate, and can effectively improve the corrosion resistance of the coating.
Description
Technical Field
The invention relates to the technical field of anti-corrosion paint, in particular to a waterborne epoxy resin anti-corrosion paint and a preparation method thereof.
Background
Metal corrosion is of great interest because it reduces the mechanical properties of the material structure, resulting in a significant amount of economic loss. Polymer coatings are considered as effective methods of reducing corrosion in complex environments, where epoxy coatings are widely used in the corrosion protection of metal substrates for their excellent corrosion resistance, electrical insulation properties and strong adhesion to metal substrates. However, during the curing of the epoxy resin, the volatilization of the solvent can create micro-holes or micro-cracks in the coating, thereby reducing the barrier and corrosion resistance of the coating. In order to improve the barrier property and corrosion resistance of the epoxy coating, a common approach is to introduce nanoparticles into the coating, so that the nanoparticles can effectively block micropores and microcracks in the coating and prevent electrolyte from diffusing to a coating/metal interface, thereby improving the corrosion resistance of the coating/metal interface.
In recent years, nano SiO 2 The epoxy resin has the excellent characteristics of high hardness, low refractive index, low cost, good light transmittance, strong scratch resistance, strong ultraviolet absorption capacity and the like, and is widely used in epoxy paint. However, due to SiO 2 The surface of the nano particle is smooth and defect-free, and the polymer and the nano SiO 2 The interface interaction force between the two is low; furthermore, nano SiO 2 The presence of a large amount of-OH on the particle surface can lead to hydrophilic nano SiO 2 Particles are incompatible with non-polar or weakly polar coating matrices, limiting their practical use in organic coatings.
Cage-shaped siloxane (POSS) is an inorganic-organic composite material with a three-dimensional nano structure, has a molecular skeleton diameter of about 1.5nm, has excellent chemical, thermal, mechanical stability, hydrophobicity and other physicochemical properties, can provide a coarse structure by being blended with a polymer or used as a covalent grafting monomer, reduces the surface energy of the material, and has good compatibility with the polymer.
POSS-CuPc-SiO of the prior art 2 Preparation method of modified epoxy resin composite material by PDA-SiO 2 Phenyl functionality of the hybrid monomer and copper (NH) amino phthalocyanine 2 -CuPc) amino functional groups undergo Michael addition reaction to obtain polyamino CuPc-SiO 2 A hybrid dielectric monomer; by polyaminoing CuPc-SiO 2 The amino functional group of the hybridized dielectric monomer and the chlorine functional group of the mono-functional group 3-chloropropyl POSS are subjected to substitution reaction to obtain POSS-CuPc-SiO 2 A hybrid dielectric monomer; with POSS-CuPc-SiO 2 The hybridization dielectric monomer is used as a filler, E51 epoxy resin is used as a polymer matrix, and the POSS-CuPc-SiO with high dielectric constant and low dielectric loss is prepared 2 Modified epoxy resin composite materials. The prior art mainly solves the technical problems of reducing leakage current and dielectric loss.
The preparation of the silicon-containing epoxy resin nanocomposite and MD simulation thereof in the prior art disclose that E51-type epoxy resin is selected, polyether amine D230 is taken as a curing agent, phenyl epoxy POSS (EP-Ph-POSS) is taken as a modified substance, an epoxy resin composite system with POSS content of 2%, 5%, 10% and 15% is prepared, and a system (E51/NH 2-Ph-POSS system) of POSS physical doping modified epoxy resin and a coupling agent modified E51/KH550+PTES (aminopropyl triethoxysilane+phenyl triethoxysilane) and E51/KH560+PTES (oxypropyl trimethoxysilane+phenyl triethoxysilane) system are simultaneously constructed. The paper research finds that the resin material modified in a chemical bonding mode has better thermal performance, is mainly applied to electronic packaging materials, and solves the technical problem of improving the thermal performance.
The self-repairing anticorrosive paint comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 20-50 parts of epoxy resin; 10-16 parts of solvent; 0.3 to 1.5 portions of dispersing agent; 0.2 to 1.5 portions of thixotropic agent; 38-56 parts of filler; 1.5 to 5.0 portions of corrosion inhibitor microcapsule; the component B comprises the following raw materials in parts by weight: 70-90 parts of curing agent; 10-30 parts of solvent. The self-repairing anticorrosive paint solves the problems that the compatibility between the corrosion inhibitor microcapsule and a coating matrix is poor, and the corrosion inhibitor carrier leaves a channel for corrosive substances after the corrosion inhibitor is released, so that more defects are brought, and the mechanical strength of the corrosion inhibitor particles is poor by loading the corrosion inhibitor into an organic/inorganic hybrid carrier and adding the corrosion inhibitor into the anticorrosive paint.
However, cage siloxanes (POSS), nano SiO, have not been used in the prior art 2 And the epoxy resin improves the barrier property and corrosion resistance of the coating, improves the corrosion resistance of a coating/metal interface and the like.
Disclosure of Invention
The invention provides a POSS modified nano SiO for solving the problems that the existing epoxy resin coating has poor corrosion resistance and can not effectively prevent electrolyte from diffusing to a coating/metal interface 2 A hybrid material;
simultaneously, providing a water-based epoxy resin anticorrosive paint;
and, providing a POSS modified nano SiO 2 A preparation method of the hybrid material; a preparation method of a water-based epoxy resin anticorrosive paint.
In order to solve the technical problems, the technical scheme of the invention is as follows:
POSS modified nano SiO 2 The preparation method of the hybrid material comprises the following steps:
step (1), adding 20-25 mL of deionized water, 8-12 mL of propanol, 2-3 mL of acetonitrile and 0.5-1 mL of tetraethylammonium hydroxide into a reaction vessel, fully mixing, slowly dropwise adding 40-60 g of 3-aminopropyl triethoxysilane into the mixed solution, and fully stirring the mixture at 50 ℃ for reaction after the dropwise adding is finished;
after the reaction is completed, cooling to room temperature, washing with cold tetrahydrofuran, precipitating white crystals, filtering, drying the white crystals at 90 ℃ to obtain NH 2 -POSS；
Step (2) adding trometamol to a reaction vessel containing deionized water and slowly adding a dilute saltAcid, adjusting the pH value of the solution to 8.5, and stirring TA and nano SiO continuously 2 Adding the solution into the solution, adding NH under rapid stirring after ultrasonic treatment for 0.5 to 1 hour 2 Continuing to carry out ultrasonic treatment on the POSS for 1-2 h, and finally stirring the mixture at room temperature for full reaction;
after the reaction is finished, standing and filtering to obtain a precipitate, washing the precipitate with deionized water, and vacuum drying the precipitate at 50-60 ℃ to obtain light yellow solid powder, namely POSS-TA-SiO 2 。
Preferably, in the step (2), tannic acid and SiO 2 And NH 2 The mass ratio of the POSS is 1:1 to 1.5:2 to 6.
Further preferably, in the step (2), tannic acid and SiO 2 And NH 2 The mass ratio of the POSS is 1:1.2:2.
the invention innovatively prepares amino-functional silsesquioxane (NH) through the hydrolytic condensation reaction of a silane coupling agent (3-aminopropyl triethoxysilane) 2 POSS), and further modifying the functional macromolecules by covalent bonds by using Tannic Acid (TA) as a multifunctional reaction center to obtain NH 2 Grafting of POSS to SiO 2 Surface, preparing POSS modified nano SiO 2 Hybrid materials (POSS-TA-SiO) 2 )。
The water-based epoxy resin anticorrosive paint is prepared from the following substances in parts by weight:
wherein the epoxy equivalent of the epoxy resin is 184-195 g/mol, and the viscosity at 25 ℃ is 10000-16000 mPa.s; POSS-TA-SiO 2 The hybrid material is the POSS modified nano SiO prepared by the invention 2 A hybrid material.
Preferably, the aqueous epoxy resin anticorrosive paint is prepared from the following substances in parts by weight:
further preferably, the aqueous epoxy resin anticorrosive paint is prepared from the following substances in parts by weight:
preferably, the water-based curing agent is a nonionic system, the content of active ingredients is 50+/-2%, the equivalent weight of active hydrogen is 230, and the viscosity at 25 ℃ is 2999-3000 mPa.s.
Preferably, the aqueous dispersing agent is an acid group copolymer solution, the solvent is propylene glycol monomethyl ether acetate/alkylbenzene, and the specific gravity is 1.01-1.05.
A preparation method of a water-based epoxy resin anticorrosive paint comprises the following steps:
adding epoxy resin and POSS-TA-SiO into deionized water 2 The solid-to-liquid ratio of the solution is controlled to be 60-70% by the hybrid material and the water-based dispersing agent, and after the mixture is stirred uniformly at a high speed of 800-1000 r/min,
and then adding the water-based curing agent, the water-based leveling agent and the water-based defoaming agent, and fully and uniformly stirring to obtain the water-based epoxy resin anticorrosive paint.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the epoxy coating of the invention can obviously improve the mechanical property, thermal property and corrosion resistance of the material by introducing POSS groups, can increase the crosslinking density and surface hydrophobicity of epoxy resin, and TA molecules serving as multifunctional reaction centers can be spontaneously oxidized into quinone compounds under alkaline conditions to further self-polymerize into TA oligomers, and have strong binding capacity with the surface of a substrate through covalent/non-covalent interaction, and nano SiO 2 The method can effectively reduce the micropore structure of the coating caused by solidification, delay the time of corrosive medium in the environment reaching the metal substrate, and effectively improve the corrosion resistance of the coating.
Through FTIR, 1 HNMR and XPS feature POSS-TA-SiO 2 Successful synthesis of the product; it was found by SEM and water contact angle display that an appropriate amount of POSS-TA-SiO was added 2 The hybrid material can be uniformly dispersed in the epoxy coating, so that the surface of the coating presents a hydrophobic structure, and the water contact angle is 119.3 degrees at maximum; salt spray tests and electrochemistry show that POSS-TA-SiO is added into the coating 2 When the epoxy composite coating is used, the epoxy composite coating has excellent corrosion resistance, and the corrosion efficiency can reach 99.1 percent at most.
Drawings
FIG. 1 is NH of example 1 2 -infrared spectrum of POSS;
FIG. 2 is NH of example 1 2 POSS 1 HNMR spectroscopy;
FIG. 3 is SiO 2 And POSS-TA-SiO of example 1 2 An infrared spectrogram;
FIG. 4 is a POSS-TA-SiO of example 1 2 Full-range XPS spectrum (a), C1s (b) and N1s (C) spectra;
FIG. 5 is SiO 2 POSS-TA-SiO from example 1 2 TGA curve of (2);
FIG. 6 shows the POSS-TA-SiO content 2 Polarization curve of the coating after 156h immersion in 3.5% wtnacl solution;
FIG. 7 shows the POSS-TA-SiO content 2 Nyquist plot (a) and Bode plot (b) of the coating immersed in 3.5% nacl solution for 156 h;
FIG. 8 is an SEM image of a broken surface of a coating;
FIG. 9 is a graph of water contact angle for a coating;
fig. 10 is a photograph of a salt spray experiment of the coating in 5% wtnacl solution.
Detailed Description
The invention will be further illustrated with reference to the drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Unless otherwise specified, the reagents and materials used in the following examples and comparative examples are all commercially available:
the epoxy equivalent of the epoxy resin is 184-195 g/mol, and the viscosity at 25 ℃ is 10000-16000 mPa.s; optionally, the epoxy resin is E-51 type, and the manufacturer has a wide range of industries;
the water-based curing agent is a nonionic system, the content of active ingredients is 50+/-2%, the equivalent weight of active hydrogen is 230, and the viscosity at 25 ℃ is 2999-3000 mPa.s; optionally, the water-based curing agent is QG-628 type, and the industry is industrial;
the water-based dispersing agent is a copolymer solution with acid groups, the solvent is propylene glycol monomethyl ether acetate/alkylbenzene, and the specific gravity is 1.01-1.05. Optionally, the aqueous dispersant is Sago-9022 type, and Germany of manufacturers is high;
the water-based leveling agent is SP-941 type, manufacturer De Feng Xiaopao;
the aqueous defoamer is DF-892 type, and is de Feng defoamer of manufacturers.
POSS modified nano SiO 2 The preparation method of the hybrid material comprises the following steps:
in the step (1), 20-25 mL of deionized water, 8-12 mL of propanol, 2-3 mL of acetonitrile and 0.5-1 mL of tetraethylammonium hydroxide are added into a reaction bottle provided with a mechanical stirring and condensing tube, 40-60 g of 3-aminopropyl triethoxysilane is slowly dripped into the mixed solution after mixing, and the mixture is stirred at 45-55 ℃ after dripping. After the reaction is completed, cooling to room temperature, washing with cold tetrahydrofuran, precipitating a large amount of white crystals, filtering, and drying the white crystals at 80-95 ℃ for 24 hours to obtain NH 2 -POSS。
Step (2) adding Tris (hydroxymethyl) aminomethane (Tris) into a reaction bottle filled with deionized water, slowly adding 0.1mol/L dilute hydrochloric acid, regulating the pH value of the solution to 8.5, and stirring tannic acid and nano SiO continuously 2 Adding the solution into the solution, adding NH under rapid stirring after ultrasonic treatment for 0.5 to 1 hour 2 Continuing to ultrasonic POSS for 1-2 h, and finally stirring the mixture at room temperature, wherein tannic acid and SiO 2 And NH 2 The mass ratio of the POSS is 1:1-1.5: 2-6, after the reaction is completed, standing and filtering to obtain a precipitate, washing the precipitate with deionized water for several times, and vacuum drying at 50-60 ℃ to obtain light yellow solid powder, namely POSS-TA-SiO 2 。
The water-based epoxy resin anticorrosive paint is prepared from the following substances in parts by weight: 30-50 parts of epoxy resin and POSS-TA-SiO 2 2 to 6 parts of hybrid material, 50 to 100 parts of water-based curing agent, 0.5 to 2 parts of water-based dispersing agent, 1 to 3 parts of water-based leveling agent and 0.5 to 1 part of water-based defoaming agent.
The epoxy equivalent of the epoxy resin is 184-195 g/mol, and the viscosity of the epoxy resin is 10000-16000 mPa.s at 25 ℃.
The water-based curing agent is a nonionic system, the content of active ingredients is 50+/-2%, the equivalent weight of active hydrogen is 230, and the viscosity at 25 ℃ is 2999-3000 mPa.s.
The water-based dispersing agent is 9022, the water-based leveling agent is SP-941, and the water-based defoaming agent is DF-892.
The preparation method of the aqueous epoxy resin anticorrosive paint comprises the following steps:
(1) Adding 30-50 parts of E51 type epoxy resin and POSS-TA-SiO into deionized water 2 2-6 parts of hybrid material, 0.5-2 parts of aqueous dispersing agent, controlling the solid-to-liquid ratio of the solution to be 60-70%, stirring uniformly at a high speed of 800-1000 r/min, adding 50-100 parts of aqueous curing agent, 1-3 parts of aqueous leveling agent and 0.5-1 part of aqueous defoaming agent, and stirring uniformly to obtain the aqueous epoxy resin anticorrosive paint.
The following specific examples were carried out according to the above-described methods.
Example 1
(1) Preparation of NH 2 POSS component 1:
in a reaction flask equipped with a mechanical stirring and condensing tube, 22.5mL of deionized water, 10mL of propanol, 2.5mL of acetonitrile and 0.5mL of tetraethylammonium hydroxide were added, and after mixing, 55.25g of KH-550 was slowly dropped into the above mixture, and after the dropping was completed, the mixture was stirred at 50℃for 24 hours. After the reaction is completed, cooling to room temperature, washing with cold tetrahydrofuran three times, precipitating a large amount of white crystals, filtering, drying the white crystals at 90 ℃ for 24 hours to obtain NH 2 -POSS。
(2) Preparation of POSS-TA-SiO 2 Component 1: 0.5g Tris was added to a reaction flask containing 300mL deionized water, and 0.1mol/L dilute hydrochloric acid was slowly added,adjusting pH to 8.5, stirring 1g Tannic Acid (TA) and 1.2g nano SiO 2 Adding into the above solution, ultrasonic treating for 0.5 hr, adding 2g NH under rapid stirring 2 The POSS is sonicated for a further 1h and finally the mixture is stirred at room temperature for 12h, wherein TA, siO 2 And NH 2 The mass ratio of the POSS is 1:1.2:2, after the reaction is finished, the mixture is stood and filtered to obtain a precipitate, the precipitate is washed with deionized water for several times, and the precipitate is dried in vacuum at 60 ℃ to obtain light yellow solid powder, namely POSS-TA-SiO 2 。
(3) Preparation of aqueous epoxy anticorrosive paint component EP10:
40 parts of epoxy resin and POSS-TA-SiO are added into deionized water 2 4 parts of hybrid material and 0.8 part of aqueous dispersing agent, controlling the solid-to-liquid ratio of the solution to be 60%, stirring uniformly at a high speed of 800r/min, adding 60 parts of aqueous curing agent, 1.5 parts of aqueous leveling agent and 0.5 part of aqueous defoaming agent, and stirring uniformly to obtain POSS-modified nano SiO doped 2 Is an aqueous epoxy anticorrosive coating EP10.
Example 2
(1) Preparation of NH 2 POSS component 2:
in a reaction flask equipped with a mechanical stirring and condensing tube, 20mL of deionized water, 8mL of propanol, 2mL of acetonitrile and 0.5mL of tetraethylammonium hydroxide were added, and after mixing, 40g of 3-aminopropyl triethoxysilane was slowly added dropwise to the above mixture, and after the addition was completed, the mixture was stirred at 45℃for 24 hours. After the reaction is completed, cooling to room temperature, washing with cold tetrahydrofuran three times, precipitating a large amount of white crystals, filtering, drying the white crystals at 80 ℃ for 24 hours to obtain NH 2 -POSS。
(2) Preparation of POSS-TA-SiO 2 Component 2:
0.5g Tris is added into a reaction bottle filled with 300mL deionized water, 0.1mol/L dilute hydrochloric acid is slowly added, the pH value of the solution is regulated to 8.5, and 1. 1gTA and 1g nano SiO are added under continuous stirring 2 Adding into the above solution, ultrasonic treating for 0.5 hr, adding 2g NH under rapid stirring 2 The POSS is sonicated for a further 1h and finally the mixture is stirred at room temperature for 12h, wherein TA, siO 2 And NH 2 Mass ratio of-POSSAfter the reaction is completed, standing and filtering to obtain a precipitate, washing the precipitate with deionized water for several times, and vacuum drying at 50 ℃ to obtain light yellow solid powder, namely POSS-TA-SiO 2 。
(3) Preparation of aqueous epoxy anticorrosive paint component EP3:
50 parts of epoxy resin and POSS-TA-SiO are added into deionized water 2 2 parts of hybrid material and 2 parts of aqueous dispersing agent, controlling the solid-to-liquid ratio of the solution to be 65%, stirring uniformly at a high speed of 1000r/min, adding 100 parts of aqueous curing agent, 3 parts of aqueous leveling agent and 1 part of aqueous defoaming agent, and stirring uniformly to obtain POSS-modified nano SiO doped 2 Is an aqueous epoxy anticorrosive coating EP3.
Example 3
(1) Preparation of NH 2 POSS component 3:
in a reaction flask equipped with a mechanical stirring and condensing tube, 25mL of deionized water, 12mL of propanol, 3mL of acetonitrile and 1mL of tetraethylammonium hydroxide were added, and after mixing, 60g of 3-aminopropyl triethoxysilane was slowly added dropwise to the above mixture, and after the addition was completed, the mixture was stirred at 55℃for 24 hours. After the reaction is completed, cooling to room temperature, washing with cold tetrahydrofuran three times, precipitating a large amount of white crystals, filtering, drying the white crystals at 95 ℃ for 24 hours to obtain NH 2 -POSS。
(2) Preparation of POSS-TA-SiO 2 And (3) a component 3:
0.5g Tris is added into a reaction bottle filled with 300mL deionized water, 0.1mol/L dilute hydrochloric acid is slowly added, the pH value of the solution is regulated to 8.5, and 1g TA and 1.5g nano SiO are added under continuous stirring 2 Adding into the above solution, ultrasonic treating for 0.5h, adding 6g NH under rapid stirring 2 The POSS is sonicated for a further 1h and finally the mixture is stirred at room temperature for 12h, wherein TA, siO 2 And NH 2 The mass ratio of the POSS is 1:1.5:6, after the reaction is finished, standing and filtering to obtain a precipitate, washing the precipitate with deionized water for a plurality of times, and vacuum drying at 60 ℃ to obtain light yellow solid powder, namely POSS-TA-SiO 2 。
(3) Preparation of aqueous epoxy anticorrosive paint component EP6:
adding 35 parts of epoxy resin and POSS-TA-SiO into deionized water 2 3 parts of hybrid material and 0.5 part of aqueous dispersing agent, controlling the solid-to-liquid ratio of the solution to be 70%, stirring uniformly at a high speed of 900r/min, adding 85 parts of aqueous curing agent, 1 part of aqueous leveling agent and 0.6 part of aqueous defoaming agent, and stirring uniformly to obtain POSS-modified nano SiO doped 2 Is an aqueous epoxy anticorrosive coating EP6.
Example 4
Preparation of aqueous epoxy anticorrosive paint component EP15:
30 parts of epoxy resin was added to deionized water using the POSS-TA-SiO of example 1 2 6 parts of hybrid material and 1.2 parts of aqueous dispersing agent, controlling the solid-to-liquid ratio of the solution to be 70%, stirring uniformly at a high speed of 1000r/min, adding 50 parts of aqueous curing agent, 2 parts of aqueous leveling agent and 0.8 part of aqueous defoaming agent, and stirring uniformly to obtain POSS-modified nano SiO doped 2 Is an aqueous epoxy anticorrosive coating EP15.
Comparative example 1
40 parts of epoxy resin and POSS-TA-SiO are added into deionized water 2 0 part of hybrid material and 0.8 part of aqueous dispersing agent, controlling the solid-to-liquid ratio of the solution to be 60%, stirring uniformly at a high speed of 800r/min, adding 60 parts of aqueous curing agent, 1.5 parts of aqueous leveling agent and 0.5 part of aqueous defoaming agent, and stirring uniformly to obtain undoped POSS modified nano SiO 2 Is an aqueous epoxy anticorrosive coating EP0.
Experimental detection
The materials of examples 1-4 and comparative example 1 were tested and characterized using methods conventional in the art, including infrared spectroscopic analysis and nuclear magnetic resonance hydrogen spectroscopy (using D 2 O is solvent to dissolve NH2-POSS, and 1HNMR test is carried out at room temperature), thermal weightlessness test, X-ray photoelectron spectroscopy test, scanning electron microscope test, contact angle test, electrochemical test and salt fog resistance test of the coating film.
NH prepared in example 1 2 FTIR and 1HNMR analysis of POSS
FIG. 1 is NH 2 -infrared spectrum of POSS. At 3355cm -1 The broad absorption peak at this point is-NH 2 Is 1126, 1030 and 760cm -1 The positions are all the stretching vibration peaks of Si-O-Si, 700cm -1 The bending vibration peak of Si-C is positioned, the position of the above peak well reflects NH 2 -structure of POSS.
FIG. 2 is NH at room temperature 2 POSS 1 HNMR spectra. 1 There are four chemical shifts in HNMR spectra of 8.02ppm (a, 2H), 2.79ppm (b, 2H), 1.64ppm (c, 2H), 0.58ppm (d, 2H), each hydrogen atom being assigned to one hydrogen atom of the same chemical environment, further supporting NH 2 Cage structure of POSS.
POSS-TA-SiO from example 1 2 FTIR analysis of (a)
FIG. 3 is SiO 2 And POSS-TA-SiO of example 1 2 And (5) infrared spectrogram. SiO (SiO) 2 In the curve, the position of the peak indicates SiO 2 Successful hydrolysis. In POSS-TA-SiO 2 In the curve, at 2933cm -1 And 2810cm -1 at-CH 3 Asymmetric stretching vibration peak of 1580-1635 cm -1 The broad absorption peak and its deformation are due to the generation of schiff base (c=n) between TA and POSS, 1348cm -1 Is the bending vibration peak of N-H, and in addition, at 1100cm -1 The position is POSS-TA-SiO 2 An absorption peak of Si-O-Si bond, which is overlapped with the C-O stretching vibration peak.
POSS-TA-SiO from example 1 2 XPS analysis of (C)
POSS-TA-SiO prepared by XPS instrument pair 2 Elemental analysis of the composition and chemical state of (C) is performed, FIG. 4 is POSS-TA-SiO, respectively 2 Full-range XPS spectrum, C1s and N1s spectra. As can be seen from FIG. a, the main elements include C1 (284.8 eV), N1 (399.6 eV), O1s (532.8 eV) and Si2p (103.7 eV)) peaks, which are equivalent to POSS-TA-SiO 2 Is consistent with the hybrid component of (a). Three sets of peaks appear in plot b, corresponding to C-C/C-H (284.8 eV), C-N/C-O (286.1 eV), C=O (288.5 eV), respectively, and two sets of peaks appear in plot C, corresponding to C-N (399.6 eV) and C=N (401.3 eV). Thus, XPS analysis was used to prepare POSS-TA-SiO 2 Further evidence is provided.
SiO 2 POSS-TA of example 1-SiO 2 TG analysis of (2)
Thermogravimetric analysis can provide a correlation of temperature change with sample mass for pure SiO 2 And POSS-TA-SiO 2 Information about thermal stability. FIG. 5 shows SiO 2 And POSS-TA-SiO 2 TG curve of (b). From FIG. 5, it can be seen that SiO 2 The weight loss ratio of (C) is 5.90%, mainly SiO 2 The surface contains a large amount of Si-OH, is easy to be wet in air, and is caused by condensation between Si-OH to Si-O-Si and water with the rise of temperature, which shows that SiO 2 Has good thermal stability. For POSS-TA-SiO 2 It can be observed that the mass loss occurs in three steps, the first stage (about 3.91%) being considered surface dehydration between 30 and 170 ℃, the second stage (about 10.51%) occurring between 170 and 400 ℃, which is attributable to the presence of TA in the last step of thermal decomposition between 400 and 800 ℃, the mass loss being about 17.19%, which is attributable to the presence of POSS. POSS-TA-SiO was demonstrated by analysis of mass loss 2 Is successful.
Composite coating polarization curve test analysis
Fig. 6 and table 1 show the potentiodynamic polarization curves of the epoxy composite coating and their corresponding parameters. In general, higher corrosion potentials or lower corrosion currents provide better corrosion protection to the substrate. EP10 coating with a corrosion current density of 5.36×10 -8 A·cm -2 Is far lower than that of bare Q235 steel (6.24X10 -6 A·cm -2 ) And pure water-based epoxy resin coating EP0 (8.83×10) -7 A·cm -2 ). Simultaneously with POSS-TA-SiO in the composite coating 2 The mass fraction of (a) and the corrosion current density are also changed, and the POSS-TA-SiO in the coating is changed 2 When the content of (C) is increased less, the corrosion current density tends to decrease, and when the POSS-TA-SiO content in the coating is further increased 2 The corrosion current density will instead increase, and the total body will show a tendency to decrease before increase.
The corrosion voltages of the coatings EP0, EP3, EP6 and EP10 are respectively-675 mV, -617mV, -562mV and-486 mV, the corrosion voltages are gradually increased, and the POSS-TA-SiO is continuously increased 2 In coatingAt the layer content, the corrosion voltage of the coating EP15 is again reduced to-571 mV.
At this time, the corrosion efficiency shows the same change trend, the corrosion efficiency of the EP10 coating can reach 99.1%, and the corrosion resistance is good. This represents nano SiO 2 The epoxy resin coating has good dispersibility, and the introduction of POSS improves the crosslinking density and hydrophobicity of the epoxy resin, so that the compactness of the epoxy resin anti-corrosion coating is enhanced, and the anti-corrosion performance of the coating is further improved.
TABLE 1 potentiodynamic polarization parameters of coatings after 156h immersion in 3.5% wtNaCl solution
Electrochemical impedance spectroscopy
The corrosion resistance of each coating was compared by performing EIS testing on the coating, and fig. 7 shows Nyquist plot (a) and Bode plot (b) of the composite coating immersed in 3.5% wtnacl solution for 156 h. FIG. 7 (a) shows the addition of various levels of POSS-TA-SiO to a neat epoxy coating 2 The Nyquist plot of (2) shows that the greater the arc of a circle, the higher the impedance modulus to corrosive media and the more excellent the corresponding coating corrosion protection. For the composition containing no POSS-TA-SiO 2 For the epoxy resin coating, the radius of the impedance arc is smaller, and the corrosion resistance is poorer; adding POSS-TA-SiO 2 After that, the radius of the capacitance impedance arc of the coating is obviously increased, wherein the radius of the EP10 coating is the largest, and the corrosion resistance is the best, which shows that the POSS-TA-SiO with good dispersion 2 The corrosion resistance of the epoxy resin can be effectively enhanced, which shows that the introduction of POSS can improve the crosslinking density and the surface hydrophobicity of the epoxy resin, enhance the adhesive force with a metal substrate, and reduce gaps in a coating structure by the interaction between the epoxy resin and the metal substrate, thereby reducing corrosive medium in the coating and greatly enhancing the corrosion resistance of the coating.
Furthermore, in Bode plot (b), the impedance modulus (|Z|) at low frequencies is often used 0.01Hz ) To evaluate the corrosion resistance of the coating. As shown in FIG. 7 (b), the pure epoxy coating Z 0.01Hz The value of (2) is the lowest, the corrosion resistance is poor, because of the small defects in the coating matrix, and the compactness and the barrier property among the internal structures of the coating are damaged. POSS-TA-SiO 2 The addition of (2) is effective to increase the impedance modulus of the coating, wherein the EP10 coating has a maximum impedance modulus value of 1.31 x 10 7 Ω·cm 2 Compared with a pure epoxy coating, the resin of the epoxy coating is improved by an order of magnitude, and the anti-corrosion performance is better, which is consistent with the result of a Nyquist diagram (a).
SEM image of coating fracture interface and contact angle analysis
FIG. 8 and FIG. 9 are respectively the addition of POSS-TA-SiO with different contents 2 SEM image and water contact angle image of the coating fracture surface of (a). From SEM image, no POSS-TA-SiO was contained 2 The fracture surface of the epoxy resin coating is smooth, a microporous structure can be generated in the curing process, and the water contact angle is 69.4 degrees and shows hydrophilicity. With POSS-TA-SiO 2 When the epoxy resin is added into an epoxy matrix, micropores and cracks generated by epoxy curing are gradually reduced until the micropores and cracks completely disappear, the microscopic morphology of the surface of the coating is obviously changed, the coating shows a micro-nano rugged structure, the roughness is increased, the water contact angle of the EP10 coating is 119.3 DEG at maximum, the coating shows better hydrophobic performance, and the POSS and SiO are shown 2 POSS can enhance the crosslinking density of epoxy resin and the compactness of the coating, so that the coating is changed from hydrophilic to hydrophobic, and SiO 2 The microporous structure of the coating caused by curing can be reduced well. The reason for the decrease of the water contact angle of the EP15 coating is that the POSS-TA-SiO in the epoxy matrix 2 Excessive content causes an increase in the aggregation probability of nanoparticles, resulting in uneven dispersion in the epoxy resin.
Coating salt spray experiment
Fig. 10 is a picture of the coated tinplate of the coatings EP0, EP3, EP6, EP10, EP15 after different salt spray times. For EP0 coating, after 30d of salt spray corrosion, the surface was severely corroded and covered by large area corrosion products, and at the same time, some microcracks and corrosion pits were also observed on the surface, indicating that the barrier effect of the coating was not ideal at this time. In useIn the process, once cracks and corrosion pits are formed, tiny channels are generated to allow corrosion medium to permeate, and along with the accumulation of the corrosion medium, the corrosion medium can directly reach the surface of the substrate, so that the occurrence of corrosion is accelerated. POSS-TA-SiO 2 The addition of the nano material improves the corrosion condition to a certain extent, and POSS-TA-SiO is added into the coating 2 The corrosion area of the surface of the coating is reduced, and particularly, the surface of the EP10 composite coating is clear and compact, has no obvious corrosion and peeling phenomena, and shows excellent corrosion resistance in a corrosive medium. This indicates that POSS-TA-SiO with ideal dispersibility 2 The nano material can fill some initial defects (such as micropores), so that the crosslinking density of the coating is improved, channels in the conductive coating are reduced, the channels are complicated, electrolytes are delayed from reaching the surface of the substrate, and the corrosion resistance of the coating is improved.
Impact strength, pencil hardness and adhesion
The aqueous epoxy resin anticorrosive paint prepared in examples 1 to 4 and comparative example 1 was uniformly stirred and then coated on the surface of the treated tin plate, the thickness of the coating film was controlled to be about 100 μm, and after curing, the impact strength, pencil hardness and adhesion of the cured film were measured according to GB/T1732-1993, GB/T6739-1996, GB/T9286-1998.
Table 2 performance comparison of waterborne epoxy anticorrosive coatings
As can be seen from Table 2, the addition of POSS-TA-SiO to the epoxy coating 2 The hybrid material can effectively improve the corrosion resistance and mechanical property of the coating due to POSS and SiO 2 POSS can enhance the crosslinking density of epoxy resin and the compactness of the coating, so that the coating is changed from hydrophilic to hydrophobic, and SiO 2 The microporous structure generated by curing of the coating can be reduced well, the time for corrosive medium in the environment to reach the metal substrate is delayed, and the corrosion resistance of the coating is improved.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. POSS modified nano SiO 2 The hybrid material is characterized in that the POSS modified nano SiO 2 The preparation method of the hybrid material comprises the following steps:
step (1), adding 20-25 mL of deionized water, 8-12 mL of propanol, 2-3 mL of acetonitrile and 0.5-1 mL of tetraethylammonium hydroxide into a reaction vessel, fully mixing, slowly dropwise adding 40-60 g of 3-aminopropyl triethoxysilane into the mixed solution, and fully stirring the mixture at 45-55 ℃ for reaction after the dropwise adding is finished;
after the reaction is completed, cooling to room temperature, washing with cold tetrahydrofuran, precipitating white crystals, filtering, and drying the white crystals at 80-95 ℃ to obtain NH 2 -POSS；
Step (2) adding the tris (hydroxymethyl) aminomethane into a reaction vessel filled with deionized water, slowly adding dilute acid, regulating the pH value of the solution to 8.5, and continuously stirring tannic acid and nano SiO 2 Adding the solution into the solution, adding NH under rapid stirring after ultrasonic treatment for 0.5 to 1 hour 2 Continuing to carry out ultrasonic treatment on the POSS for 1-2 h, and finally stirring the mixture at room temperature for full reaction;
after the reaction is finished, standing and filtering to obtain a precipitate, washing the precipitate with deionized water, and vacuum drying the precipitate at 50-60 ℃ to obtain light yellow solid powder, namely POSS-TA-SiO 2 。
2. The POSS modified nano SiO according to claim 1 2 A hybrid material characterized in that tannic acid and SiO in the step (2) 2 And NH 2 The mass ratio of the POSS is 1:1 to 1.5:2 to 6.
3. The POSS modified nano SiO according to claim 1 2 A hybrid material characterized in that tannic acid and SiO in the step (2) 2 And NH 2 The mass ratio of the POSS is 1:1.2:2.
4. a POSS modified nano SiO according to any one of claims 1-3 2 The preparation method of the hybrid material is characterized by comprising the following steps: the method comprises the following steps:
step (1), adding 20-25 mL of deionized water, 8-12 mL of propanol, 2-3 mL of acetonitrile and 0.5-1 mL of tetraethylammonium hydroxide into a reaction vessel, fully mixing, slowly dropwise adding 40-60 g of 3-aminopropyl triethoxysilane into the mixed solution, and fully stirring the mixture at 45-55 ℃ for reaction after the dropwise adding is finished;
after the reaction is completed, cooling to room temperature, washing with cold tetrahydrofuran, precipitating white crystals, filtering, and drying the white crystals at 80-95 ℃ to obtain NH 2 -POSS；
Step (2) adding the tris (hydroxymethyl) aminomethane into a reaction vessel filled with deionized water, slowly adding dilute acid, regulating the pH value of the solution to 8.5, and continuously stirring tannic acid and nano SiO 2 Adding the solution into the solution, adding NH under rapid stirring after ultrasonic treatment for 0.5 to 1 hour 2 Continuing to carry out ultrasonic treatment on the POSS for 1-2 h, and finally stirring the mixture at room temperature for full reaction;
after the reaction is finished, standing and filtering to obtain a precipitate, washing the precipitate with deionized water, and vacuum drying the precipitate at 50-60 ℃ to obtain light yellow solid powder, namely POSS-TA-SiO 2 。
5. The water-based epoxy resin anticorrosive paint is characterized by being prepared from the following substances in parts by weight:
wherein the epoxy equivalent of the epoxy resin is 184-195 g/mol, and the viscosity at 25 ℃ is 10000-16000 mPa.s;
the POSS-TA-SiO 2 The hybrid material is POSS-TA-SiO according to any one of claims 1 to 2 2 A hybrid material.
6. The aqueous epoxy resin anticorrosive paint according to claim 5, which is prepared from the following substances in parts by weight:
7. the aqueous epoxy resin anticorrosive paint according to claim 6, which is prepared from the following substances in parts by weight:
8. the aqueous epoxy resin anticorrosive paint according to claim 5, wherein the aqueous curing agent is a nonionic system, the content of active ingredients is 50+/-2%, the active hydrogen equivalent is 230, and the viscosity at 25 ℃ is 2999-3000 mPa.s.
9. The aqueous epoxy resin anticorrosive paint according to claim 5, wherein the aqueous dispersant is an acid group-containing copolymer solution, and the solvent is propylene glycol monomethyl ether acetate/alkylbenzene, and the specific gravity is 1.01-1.05.
10. The method for preparing the aqueous epoxy resin anticorrosive paint according to claim 5, comprising the following steps:
adding epoxy resin and POSS-TA-SiO into deionized water 2 The solid-to-liquid ratio of the solution is controlled to be 60-70% by the hybrid material and the water-based dispersing agent, and after the mixture is stirred uniformly at a high speed of 800-1000 r/min,
and then adding the water-based curing agent, the water-based leveling agent and the water-based defoaming agent, and fully and uniformly stirring to obtain the water-based epoxy resin anticorrosive paint.
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