CN113754891B - Poly (3, 4-ethylenedioxythiophene)/polyethyleneimine modified water-based epoxy emulsion, preparation method thereof and anticorrosive paint - Google Patents
Poly (3, 4-ethylenedioxythiophene)/polyethyleneimine modified water-based epoxy emulsion, preparation method thereof and anticorrosive paint Download PDFInfo
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- CN113754891B CN113754891B CN202111181297.2A CN202111181297A CN113754891B CN 113754891 B CN113754891 B CN 113754891B CN 202111181297 A CN202111181297 A CN 202111181297A CN 113754891 B CN113754891 B CN 113754891B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The invention relates to the technical field of high molecular polymer new materials. In particular to a poly 3, 4-ethylenedioxythiophene/polyethyleneimine modified waterborne epoxy emulsion, a preparation method thereof and an anticorrosive coating. The preparation method comprises the following steps: mixing a 3, 4-ethylenedioxythiophene monomer and a solvent, adding an initiator, and stirring for reaction to prepare a poly (3, 4-ethylenedioxythiophene) dispersion liquid; mixing polyethyleneimine and waterborne epoxy resin, and stirring to prepare a polyethyleneimine modified waterborne epoxy resin emulsion; and mixing the poly 3, 4-ethylenedioxythiophene dispersion liquid, the polyethyleneimine modified waterborne epoxy resin emulsion and an auxiliary agent, and shearing and emulsifying. The PEDOT/PEI modified waterborne epoxy emulsion prepared by the preparation method improves the dispersion stability of the PEDOT in the waterborne epoxy emulsion. The anticorrosive coating prepared from the PEDOT/PEI modified waterborne epoxy emulsion has excellent anticorrosive performance and good dispersion stability.
Description
Technical Field
The invention belongs to the technical field of high-molecular polymer new materials, and particularly relates to a poly (3, 4-ethylenedioxythiophene)/polyethyleneimine modified water-based epoxy emulsion, a preparation method thereof and an anticorrosive coating.
Background
The anticorrosive paint is a paint which is widely applied in modern industry, traffic, energy, ocean engineering and other departments. With the rapid development of national economy and industrialization, the annual consumption of steel in China is increasing, and steel is widely used in the fields of chemical engineering, petroleum, metallurgy, machinery, light industry, ocean engineering, ships and warships and the like, particularly in the fields of metallurgy, chemical engineering, petroleum and ocean engineering. According to the report, the steel demand in China in 2019 is 8 hundred million tons, the yield of crude steel is 9 hundred million tons, the total amount of steel corrosion per year accounts for 10-20% of the annual yield, and the economic loss caused by corrosion per year is huge. Meanwhile, in some special fields such as electric power transportation, storage tanks and pipelines, metal materials are required to have corrosion resistance and good conductive properties. Therefore, there is a need for urgent innovation in the field of metal corrosion prevention.
The conductive polymer has the advantages of easy synthesis, good environmental stability, obvious corrosion resistance effect, environmental protection and the like in the application of metal corrosion resistance, so that the materials gradually expose corners and occupy a place in the field of metal corrosion resistance, particularly in the research aspect of anticorrosive coatings. Polyaniline and polypyrrole are used for metal corrosion prevention, the research is more and the method is mature, and the research on the polythiophene conductive polymer with the same excellent performance for metal corrosion prevention is relatively less. The poly-3, 4-ethylenedioxythiophene (PEDOT) as a representative of polythiophene conductive polymers has unique chemical properties, and can improve the corrosion resistance of the water-based paint. However, pure PEDOT has extremely poor solubility, which results in poor dispersibility of PEDOT in the coating, and this defect seriously affects the application of PEDOT in metal corrosion prevention. Therefore, the application value and the corrosion prevention effect of the PEDOT as a representative of polythiophene conductive polymers in metal corrosion prevention are in urgent need of further research and study.
Disclosure of Invention
Based on the above, the invention provides a preparation method of the PEDOT/Polyethyleneimine (PEI) modified waterborne epoxy emulsion, which improves the dispersion stability of the PEDOT in the waterborne epoxy emulsion, and the anticorrosive coating prepared from the PEDOT/PEI modified waterborne epoxy emulsion has excellent anticorrosive performance.
The technical scheme is as follows:
a preparation method of PEDOT/PEI modified waterborne epoxy emulsion comprises the following steps:
mixing a 3, 4-Ethylenedioxythiophene (EDOT) monomer and a solvent, adding an initiator, and stirring for reaction to prepare a PEDOT dispersion liquid;
mixing PEI and waterborne epoxy resin, and stirring to prepare PEI modified waterborne epoxy resin emulsion;
and mixing the PEDOT dispersion liquid, the PEI modified waterborne epoxy resin emulsion and an auxiliary agent, and shearing and emulsifying to prepare the PEDOT/PEI modified waterborne epoxy emulsion.
In one embodiment, the PEI has a number average molecular weight of 600 to 10000.
In one embodiment, the PEI has a number average molecular weight selected from one of 600, 1000, 1500, 2000, 4000, 7000, and 10000.
In one embodiment, the solid content of the poly 3, 4-ethylenedioxythiophene/polyethyleneimine modified aqueous epoxy emulsion is 0.5% -12%.
In one embodiment, the mass ratio of the EDOT, the solvent and the initiator is (1-4): (20-80): (1-2).
In one embodiment, the stirring reaction time is 1-10 hours, and the stirring reaction temperature is 20-100 ℃.
In one embodiment, the initiator is selected from one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.
In one embodiment, the solvent is a mixture of an alcohol selected from one of methanol, ethanol, and propanol and water.
In one embodiment, the mass ratio of the PEI to the waterborne epoxy resin is 1: (10-20).
In one embodiment, the waterborne epoxy resin is selected from one or more of epoxy resins E-51, E-44, E-20, E-13, and E-12.
In one embodiment, the adjuvant comprises an antifoaming agent and water.
In one embodiment, the particle size of the PEDOT in the PEDOT nano dispersion liquid is 30nm to 100 nm.
The invention also provides a PEDOT/PEI modified waterborne epoxy emulsion prepared by the preparation method of the PEDOT/PEI modified waterborne epoxy emulsion.
The invention also provides an anticorrosive paint.
The raw materials of the anticorrosive paint comprise a component A and a component B;
the component A is mainly prepared from the following raw materials in parts by mass:
the component B is mainly prepared from the following raw materials in parts by mass:
60-70 parts of a water-based epoxy curing agent.
In one embodiment, the preparation method of the graphene dispersion liquid comprises the following steps:
mixing graphene, carboxymethyl cellulose and water, and shearing and dispersing for 1-2 hours to obtain a mixture;
and carrying out ultrasonic treatment on the mixture for 3-4 hours to obtain the graphene dispersion liquid.
In one embodiment, the mass fraction of graphene in the graphene dispersion liquid is 0.2-2%.
In one of the embodiments, the filler is selected from one or more of an anti-rust pigment, a coloring pigment, and an extender pigment;
the antirust pigment is selected from one or more of mica iron oxide ash, aluminum tripolyphosphate, zinc phosphate and zinc powder;
the coloring pigment is selected from one of permanent orange pigment and titanium pigment;
the extender pigment is selected from one or more of barium sulfate, mica powder, hydrated magnesium silicate, fumed silica and inorganic bentonite.
In one embodiment, the aqueous auxiliary agent is a mixture of a wetting agent, a dispersing agent, a thixotropic agent, an anti-settling agent, an antifoaming agent and a leveling agent;
in one embodiment, the wetting agent is selected from one or both of BYK-154 and BYK-192.
In one embodiment, the dispersant is PE-100.
In one embodiment, the antifoaming agent is BYK-028.
In one embodiment, the leveling agent is one or both of BYK-346 and BYK-381.
In one embodiment, the aqueous epoxy curing agent is selected from one of polyamide, fatty amine, phenolic amine, and polyetheramine.
In one embodiment, the mass ratio of the component A to the component B is (2-10): 1.
compared with the prior art, the invention has the following beneficial effects:
according to the invention, firstly, a PEDOT dispersion liquid is prepared, then PEI is added into the waterborne epoxy resin to prepare PEI modified epoxy resin emulsion, and then the PEDOT dispersion liquid is added into the PEI modified epoxy resin emulsion to carry out shearing emulsification treatment, so that the PEDOT/PEI modified waterborne epoxy emulsion is prepared. On one hand, the waterborne epoxy resin is modified by PEI, so that the corrosion resistance of the epoxy resin can be obviously improved, and the corrosion resistance of the finally prepared coating is improved. The main reason is that the primary amine, secondary amine and other active amines of PEI can generate ring-opening polymerization reaction with epoxy groups in epoxy resin, so that the epoxy resin forms a three-dimensional network structure, corrosion media can be prevented from permeating into a matrix in a corrosion environment, the diffusion rate of the corrosion media is slowed down, and the diffusion path becomes tortuous, thereby effectively improving the corrosion resistance of the coating. On the other hand, PEI is a water-soluble polyamine that effectively improves the solubility of PEDOT, so that the PEDOT dispersion is added to the PEI-modified aqueous epoxy resinWhen the PEI is in the grease emulsion, the PEDOT can be promoted to be better dispersed in the PEI modified waterborne epoxy resin emulsion, so that the PEDOT nano particles are not easy to agglomerate, and the stable PEDOT/PEI modified waterborne epoxy emulsion is formed. Furthermore, PEDOT plays an important role in resisting attack of oxygen and corrosive ions on metals. This is mainly due to the fact that the positively charged PEDOT framework can intercept chloride anions that cause pitting by damaging the passivation layer and trap electrons in the Fe and Fe (ii) oxidation reactions. Meanwhile, PEDOT can provide electrons for oxygen to be reduced into hydroxyl ions. In a word, PEDOT participates in the intermediate reaction of the metal corrosion process, plays the role of a catalyst as a medium of electron exchange, and can effectively inhibit Fe 2+ And corrosive ions such as Cl - 、O 2- Diffusion in the oxide layer on the surface of the metal slows down the corrosion rate of the metal. Therefore, when the PEDOT is stably dispersed in the PEI modified waterborne epoxy emulsion, the excellent corrosion resistance of the PEDOT can be more effectively exerted in the finally prepared coating. According to the invention, the PEDOT/PEI modified waterborne epoxy emulsion prepared by the preparation method is used as a raw material to prepare the anticorrosive coating, the obtained coating is in a uniformly dispersed state, and a coating obtained from the coating does not foam and crack and has corrosion of grade 2 or less in a neutral salt spray resistance test of not less than 2000h, so that the excellent anticorrosive performance of corrosion grade 1 is achieved.
In addition, the pencil hardness of the coating obtained by the coating can reach 6H, the adhesive force is 18MPa, the flexibility is 1mm, the coating can resist 10% HCl 30d, 10% H2SO 430 d and 92# gasoline 30d, the neutral salt spray resistance test is 2500H, and the impact resistance can reach 50cm, SO that the technical quality indexes of the epoxy anticorrosive coating and the coating are met and superior.
Drawings
FIG. 1 is a graph of the infrared spectrum of PEDOT prepared in example 1;
fig. 2 is a raman spectrum of PEDOT prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of PEDOT/PEI modified waterborne epoxy emulsion, which comprises the following steps:
s101: mixing EDOT monomer and solvent, adding initiator, stirring to react, and preparing to obtain PEDOT dispersion liquid.
Further, in step S101, the mass ratio of EDOT, solvent and initiator is (1-4): (20-80): (1-2).
Further, in step S101, the initiator is one or more selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate.
Further, in step S101, the solvent is a mixture of alcohol and water; the alcohol is selected from one or more of methanol, ethanol and propanol.
Further, in step S101, the stirring reaction time is 1 to 10 hours, the stirring reaction temperature is 20 to 100 ℃, and further, the reaction temperature is 25 ℃.
Further, in step S101, the particle size of PEDOT in the PEDOT dispersion is 30 to 100 nm.
In the invention, the PEDOT dispersion liquid is prepared through in-situ polymerization reaction, namely EDOT is used as a monomer for reaction, persulfate is used as an initiator for reaction, and a mixed solution of alcohol and water is used as a continuous phase for reaction. Because the performed polymers of EDOT and EDOT can be dissolved in the continuous phase, and the polymer is insoluble in the continuous phase, the PEDOT nanoparticles gradually deposit in the continuous phase after the performed polymers are gradually polymerized into the PEDOT nanoparticles, and then the PEDOT nanoparticles are stirred to form PEDOT dispersion liquid, wherein the PEDOT nanoparticles are used as a powerful reinforcing agent for the corrosion resistance of the subsequently prepared anticorrosive paint. Further, the structural formula of PEDOT is shown in formula 1. In this formula, both the 3-and 4-positions are substituted with pendant ether linkages, and polymerization can only occur at the 2-and 5-positions, so that the resulting polymer is a linear polymer.
S102: and mixing the PEI and the waterborne epoxy resin, and stirring to prepare the PEI modified waterborne epoxy resin emulsion.
Further, in step S102: the number average molecular weight of PEI is 600-10000. Specifically, the number average molecular weight of PEI is selected from one of 600, 1000, 1500, 2000, 4000, 7000, and 10000.
Further, in step S102: the mass ratio of the PEI to the waterborne epoxy resin is 1: (10-20). Specifically, the mass ratio of PEI to waterborne epoxy includes, but is not limited to, 1: 10. 1:12, 1:15, 1:18, 1: 20.
Further, in step S102: the water-based epoxy resin is bisphenol A epoxy resin, and further, the bisphenol A epoxy resin is selected from one or more of epoxy resins E-51, E-44, E-20, E-13 and E-12.
Further, in step S102: the stirring reaction temperature is 20-60 ℃, and further, the reaction temperature is 25 ℃.
According to the invention, PEI with different molecular weights can be added into the waterborne epoxy resin, and the waterborne epoxy resin is stirred for reaction to prepare the PEI modified waterborne epoxy emulsion. The formulas 2 and 3 are respectively the structural formula of the bisphenol A epoxy resin and the structural formula of PEI, and it can be seen that the bisphenol A epoxy resin has active hydroxyl and epoxy groups, and the PEI structure has active amino groups such as primary amine and secondary amine. The formula 4 is the structural formula of the PEI modified waterborne epoxy resin prepared by the preparation method, wherein m is about 600, and n is more than or equal to 1000. Wherein the end-ring oxygen group in the bisphenol A epoxy resin is subjected to ring opening and is respectively subjected to polymerization reaction with primary amine and secondary amine active amine in PEI, so that the epoxy resin forms a three-dimensional network structure. The three-dimensional reticular structure can prevent corrosive media from permeating into a matrix in a corrosive environment, slow down the diffusion rate of the corrosive media and lead the diffusion path to become tortuous, thereby effectively improving the corrosion resistance of the coating.
S103: and mixing the PEDOT nano dispersion liquid, the PEI modified waterborne epoxy resin emulsion and the auxiliary agent, and shearing and emulsifying to prepare the PEDOT/PEI modified waterborne epoxy emulsion.
Further, in step S103, the solid content of the PEDOT/PEI modified waterborne epoxy emulsion is 0.5% to 12%.
Further, in step S103, the auxiliary agent includes an antifoaming agent and water.
It is understood that the PEDOT nanodispersion, the PEI modified waterborne epoxy resin emulsion and the auxiliary agent may be mixed with stirring.
In the invention, because PEDOT plays an important role in resisting the attack of oxygen and corrosive ions to metals, the key factors influencing PEDOT as a powerful reinforcing agent for the anticorrosion performance of the coating are as follows: PEDOT has poor solubility and dispersibility. On one hand, PEDOT in this application is in the form of nanoparticles, which cannot be uniformly dispersed in the base material due to large specific surface area and are prone to agglomeration, and on the other hand, PEDOT has poor solubility in the base material due to its nature. Furthermore, the solubility and dispersibility of PEDOT also affect the uniformity of the coating. Therefore, it is very important to improve the dispersibility of PEDOT in the solution. Since PEI is a water-soluble polyamine and has good dispersibility, the solubility of PEDOT can be effectively improved, so when the PEDOT nano dispersion liquid is added into the PEI modified waterborne epoxy resin emulsion, PEI can promote PEDOT to be better dispersed in the PEI modified waterborne epoxy resin emulsion, PEDOT is not easy to agglomerate, and stable PEDOT/PEI modified waterborne epoxy emulsion is formed.
The invention also provides the PEDOT/PEI modified waterborne epoxy emulsion prepared by the preparation method of the PEDOT/PEI modified waterborne epoxy emulsion.
The invention also provides an anticorrosive paint which comprises the raw materials of the component A and the component B;
the component A is mainly prepared from the following raw materials in parts by mass:
the component B is mainly prepared from the following raw materials in parts by mass:
60-70 parts of a water-based epoxy curing agent.
Further, the preparation method of the graphene dispersion liquid comprises the following steps:
mixing graphene, carboxymethyl cellulose and water, and shearing and dispersing for 1-2 hours to obtain a mixture;
carrying out ultrasonic treatment on the mixture for 3-4 hours to obtain graphene dispersion liquid;
in one embodiment, the mass fraction of graphene in the graphene dispersion liquid is 0.2-2%.
Further, the filler is selected from one or more of an anti-rust pigment, a coloring pigment and an extender pigment;
the antirust pigment is selected from one or more of mica iron oxide ash, aluminum tripolyphosphate, zinc phosphate and zinc powder;
the coloring pigment is selected from one of permanent orange pigment and titanium dioxide;
the extender pigment is selected from one or more of barium sulfate, mica powder, hydrated magnesium silicate, fumed silica and inorganic bentonite.
Further, the aqueous auxiliary agent is a mixture of a wetting agent, a dispersing agent, a thixotropic agent, an anti-settling agent, an antifoaming agent and a leveling agent.
The wetting agent is selected from one or two of BYK-154 and BYK-192; the amount of the (B) is 0.5 to 1 part by weight.
The dispersing agent is PE-100.
The defoaming agent is BYK-028.
The leveling agent is one or two of BYK-346 and BYK-381, and the weight part of the leveling agent can be 0.2-2 parts.
It should be noted that the auxiliary agents described in the present invention can be selected from the auxiliary agents conventional in the art, and the present invention is not further described herein.
Furthermore, the anticorrosive paint of the invention can also be added with a cosolvent.
The cosolvent is selected from one or more of Dimethylformamide (DMF), dimethylacetamide (DMAc) and methylpyrrolidone (NMP).
Further, the waterborne epoxy curing agent is selected from one of polyamide, fatty amine, phenolic amine and polyether amine.
When the paint is used, the component A and the component B are mixed according to the mass ratio of (2-10): 1, mixing.
Furthermore, the component A and the component B are mixed according to the mass ratio of (2-5): 1.
The invention also provides a preparation method of the anticorrosive paint.
The specific technical scheme is as follows:
a preparation method of an anticorrosive paint comprises the following steps:
mixing the PEDOT/PEI modified waterborne epoxy emulsion, the graphene dispersion liquid, the filler, the waterborne auxiliary agent and water, dispersing for 20-30 min on a high-speed dispersion machine, grinding on a sand mill, filtering, and subpackaging to obtain a component A;
the waterborne epoxy curing agent is used as a component B;
mixing the A component and the B component.
After grinding, the fineness of the filler in the mixture is 15-30 μm.
It is understood that when preparing the B component, water can be added to the water-based epoxy curing agent for dilution.
According to the invention, PEI is adopted to improve the corrosion resistance of epoxy resin and paint, and simultaneously, PEDOT nanoparticles prepared by in-situ polymerization are promoted to be dispersed in PEI modified epoxy resin emulsion, so that the dispersion stability of PEDOT in aqueous epoxy emulsion is improved, the important function of PEDOT in resisting the attack of oxygen and corrosive ions on metal can be more effectively exerted, and PEDOT is used as a powerful reinforcing agent for the corrosion resistance of subsequent anticorrosive paint. According to the invention, the synergistic effect of PEDOT, PEI and waterborne epoxy resin is utilized, so that the corrosion resistance of the obtained coating can be obviously improved. The coating obtained from the coating has no bubbling and cracking and no corrosion of grade 2 in a neutral salt spray resistance test of more than or equal to 2000h, and achieves excellent corrosion resistance of grade 1. And the obtained coating material is in a stable state with uniform dispersion.
The following is a further description with reference to specific examples.
The aqueous epoxy curing agent has a high viscosity when the solid content is 100%, so that the aqueous epoxy curing agent diluted to 60-70% by using 30-40 parts of water is usually used only when the aqueous epoxy curing agent is stirred at 1500-2000 rpm for 1-2 h. The polyether amine BASF BS-725 selected in each example and comparative example is a waterborne epoxy curing agent diluted to 70% solid content and is a finished curing agent, so that 30-40 parts of water is not required to be added for dilution.
Example 1
The embodiment provides a poly 3, 4-ethylenedioxythiophene/polyethyleneimine modified waterborne epoxy emulsion and a preparation method thereof, and the preparation method specifically comprises the following steps:
(1) preparation of PEDOT Dispersion
Firstly, 2g of EDOT monomer is dissolved in a mixed solution composed of 20ml of alcohol and 20ml of water, then 0.5g of ammonium persulfate is added, the mixture is fully stirred and stirred for 1 hour, and then PEDOT dispersion liquid is prepared, wherein the infrared spectrogram of the prepared PEDOT is shown in figure 1, and the Raman spectrogram of PEDOT nano-particles is shown in figure 2.
With reference to FIGS. 1 and 2, the infrared spectrum of PEDOT in FIG. 1 shows a wavelength of 721 -1 、862 -1 、995cm -1 C-S stretching vibrator in thiophene ringA characteristic peak of motility; wavelength of 1062 -1 、1123 -1 、1165cm -1 Is the absorption peak of C-O-C bending vibration in PEDOT; wavelength 1265 -1 、1499cm -1 The positions are respectively the characteristic peaks of C-C and C ═ C stretching vibration in the thiophene ring. As can be seen from the Raman spectrum of PEDOT in FIG. 2, it is located at 1426cm -1 The characteristic peak belongs to C on a single five-membered thiophene ring in the PEDOT main chain α ＝C β The symmetric stretching vibration of (2).
This procedure was seen to successfully prepare PEDOT.
(2) Preparation of PEI modified waterborne epoxy resin emulsion
5g of PEI with the number average molecular weight of 600 is added into 50g of waterborne epoxy resin E-20, and after the reaction is fully stirred for 1 hour, the PEI modified waterborne epoxy resin emulsion is prepared.
(3) Preparation of PEDOT/PEI modified waterborne epoxy emulsion
Adding 5g of PEDOT dispersion liquid prepared in the step 1) into the PEI modified waterborne epoxy resin emulsion prepared in the step 2), adding 1g of BYK-028 defoaming agent and 20g of water, mixing, stirring at a high speed, shearing and emulsifying to obtain the PEDOT/PEI modified waterborne epoxy emulsion with the solid content of about 1%.
Example 2
The embodiment provides an anticorrosive paint (primer) and a preparation method thereof, and the preparation method comprises the following steps:
(1) preparation of component A
450g of PEDOT/PEI modified waterborne epoxy emulsion prepared in example 1, 10g of BYK-154 wetting dispersant, 5g of BYK-028 defoaming agent, 5g of BYK-381 leveling agent, 150g of mica iron oxide ash, 80g of aluminum tripolyphosphate, 80g of zinc phosphate, 100g of 3000-mesh barium sulfate, 10g of Pangel B40 hydrated magnesium silicate, 10g of A200 fumed silica and 100g of purified water are mixed, stirred and dispersed on a high-speed dispersion machine for 20-30 min, ground by a sand mill, the particle size of a filler in the ground mixture is 25-30 mu m, filtered and subpackaged to obtain a component A.
(2) Preparation of component B
And (3) subpackaging 200g of the polyether amine BASF BS-725 waterborne epoxy curing agent to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 5: 1 to obtain the PEDOT/PEI modified waterborne epoxy anticorrosive paint which is used as a primer.
Example 3
The embodiment provides an anticorrosive paint (finish paint) and a preparation method thereof, and the preparation method comprises the following steps:
600g of PEDOT/PEI modified waterborne epoxy emulsion prepared in example 1, 10g of BBYK-154 wetting dispersant, 5g of BYK-028 defoaming agent, 5g of BYK-381 leveling agent, 160g of permanent orange pigment, 100g of 1200-mesh mica powder, 10g of Pangel B20 hydrated aluminum magnesium silicate, 10g of A200 fumed silica and 100g of purified water are mixed, stirred and dispersed on a high-speed dispersing machine for 20-30 min, ground by a sand mill, filtered, and subpackaged to obtain a component A, wherein the particle size of a filler in the ground mixture is 15-25 mu m.
(2) Preparation of component B
And (3) subpackaging 250g of the polyether amine BASF BS-725 waterborne epoxy curing agent to obtain the component B.
When the waterborne epoxy anti-corrosion coating is used, the component A and the component B are mixed according to the mass ratio of 4: 1 to obtain the PEDOT/PEI modified waterborne epoxy anti-corrosion coating which is used as a finish.
Example 4
The embodiment provides an anticorrosive paint (primer) and a preparation method thereof, and the preparation method comprises the following steps:
(1) preparation of graphene dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5 hours to obtain a mixture.
And (3) carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 1.5%.
(2) Preparation of component A
By mass, 40 parts of PEDOT/PEI modified waterborne epoxy emulsion prepared in example 1, 5 parts of graphene dispersion prepared in step 1), 1 part of inorganic bentonite, 5 parts of 800-mesh mica powder, 0.5 part of BYK-192 wetting agent, 0.5 part of PE-100 dispersing agent, 0.5 part of BYK-346 flatting agent, 0.5 part of BYK-028 defoaming agent, 1 part of fumed silica, 1 part of hydrated magnesium silicate and 5 parts of purified water are mixed, stirred and dispersed for 30min on a high-speed dispersion machine, ground by a sand mill, the particle size of a filler in the ground mixture is 15-25 mu m, then 40 parts of 800-mesh zinc powder is added, and after 20-30 min of low-speed dispersion, filtration and subpackaging are carried out, so as to obtain component A.
(3) Preparation of component B
And (3) subpackaging 20 parts of the BASF BS-725 waterborne epoxy curing agent by mass to obtain a component B.
When the epoxy resin primer is used, the component A and the component B are mixed according to the mass ratio of 5: 1 to obtain the PEDOT/PEI modified waterborne epoxy anticorrosive paint which is used as a primer and is an electrostatic conductive paint primer. The coating and coating properties are shown in Table 1.
Example 5
The embodiment provides an anticorrosive paint (finish paint) and a preparation method thereof, and the preparation method comprises the following steps:
(1) preparation of graphene dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5 hours to obtain a mixture.
And (3) carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 1.5%.
(5) Preparation of component A
By mass, 60 parts of PEDOT/PEI modified waterborne epoxy emulsion prepared in example 1, 20 parts of titanium dioxide, 6 parts of graphene dispersion prepared in step 1), 1 part of PE-100 dispersing agent, 0.5 part of BYK-346 leveling agent, 0.5 part of BYK-028 defoaming agent, 1 part of fumed silica, 1 part of hydrated magnesium silicate and 10 parts of purified water are mixed, stirred and dispersed for 20min on a high-speed dispersion machine, ground by a sand mill, the particle size of a filler in the ground mixture is 15-25 μm, filtered and subpackaged to obtain a component A.
(4) Preparation of component B
And (3) subpackaging 25 parts of the BASF BS-725 waterborne epoxy curing agent to obtain the component B.
When the epoxy resin anti-corrosion coating is used, the component A and the component B are mixed according to the mass ratio of 4: 1 to obtain the PEDOT/PEI modified waterborne epoxy anti-corrosion coating, and the coating is used as a finish paint and is a static conductive coating primer. The coating and coating properties are shown in Table 1.
TABLE 1
In examples 4 and 5, because PEDOT has the ability of being oxidized again and the oxidation potential of PEDOT is lower than that of graphene, a conductive network can be formed between PEDOT and graphene, so that graphene can play an electrochemical protection role on steel, and finally, the prepared coating has enhanced corrosion resistance and excellent conductivity of graphene.
Comparative example 1
The comparative example provides an anticorrosive coating (primer) and a preparation method thereof, which are basically the same as example 4, and mainly differ in that a PEDOT/PEI modified waterborne epoxy emulsion is not used in the component A, and the specific steps are as follows:
(1) preparation of component A
By mass, 40 parts of south Asia CYD-115 water-based epoxy resin, 5 parts of graphene dispersion liquid, 1 part of inorganic bentonite, 5 parts of 800-mesh mica powder, 0.5 part of BYK-192 wetting agent, 0.5 part of PE-100 dispersing agent, 0.5 part of BYK-346 leveling agent, 0.5 part of BYK-028 defoaming agent, 1 part of fumed silica, 1 part of hydrated magnesium silicate and 5 parts of purified water are mixed, stirred and dispersed for 30min on a high-speed dispersion machine, ground by a sand mill, the particle size of a filler in the ground mixture is 15-25 mu m, then 40 parts of 800-mesh zinc powder is added, and after 20-30 min of low-speed dispersion, filtration and subpackaging are carried out to obtain the component A.
(2) Preparation of component B
And (3) subpackaging 20 parts of the BASF BS-725 waterborne epoxy curing agent by mass to obtain a component B.
When the static conductive primer is used, the component A and the component B are mixed according to the mass ratio of 5: 1 to obtain the static conductive primer. The coating and coating properties are shown in Table 2.
Comparative example 2
The comparative example provides an anticorrosive coating (finish) and a preparation method thereof, which are basically the same as the example 5, and mainly differ in that the component A does not use PEDOT/PEI modified waterborne epoxy emulsion, and the specific steps are as follows:
(1) preparation of component A
Mixing 60 parts of south Asia CYD-115 waterborne epoxy resin, 20 parts of titanium dioxide, 6 parts of graphene dispersion liquid, 1 part of PE-100 dispersing agent, 0.5 part of BYK-346 leveling agent, 0.5 part of BYK-028 defoaming agent, 1 part of fumed silica, 1 part of hydrated magnesium silicate and 10 parts of purified water in parts by mass, stirring and dispersing for 20min on a high-speed dispersion machine, grinding by a sand mill, enabling the particle size of fillers in the ground mixture to be 15-25 mu m, filtering and subpackaging to obtain the component A.
(2) Preparation of component B
And (3) subpackaging 25 parts of the BASF BS-725 waterborne epoxy curing agent to obtain the component B.
When the static conductive primer is used, the component A and the component B are mixed according to the mass ratio of 4: 1 to obtain the static conductive primer. The coating and coating properties are shown in Table 3.
TABLE 2
TABLE 3
In tables 1-3, the methods for each property test are as follows
1. The pencil hardness is tested according to the GB/T6739-;
2. the adhesion force is tested according to the GB/T1720-;
3. flexibility is tested according to GB/T1720-79 standard;
4. impact resistance was tested according to GB/T1732 + 1993 standard;
5. the boiling water resistance is tested according to the GB/T1733-93 standard;
6. the acid and alkali resistance is tested according to the GB/T1763 standard;
7. gasoline resistance was tested according to GB/T1734 + 1993 standard;
8. the salt spray resistance is tested according to the GB/T1771-91 standard;
tables 4 and 5 show the technical indexes of the coating and the obtained coating in the field of modified anticorrosive coatings.
TABLE 4
TABLE 5
It can be seen that in Table 1, the properties of the coatings of examples 4-5 and the resulting coatings meet the specifications of tables 4-5. The coating is in a uniformly dispersed state in the container, and the coating does not bubble and crack in a neutral salt spray resistance test for more than or equal to 2000h, and achieves excellent corrosion resistance of corrosion grade 1. Table 2 shows the comparison of the performances of the coating and the obtained coating in example 4 and comparative example 1, and Table 3 shows the comparison of the performances of the coating and the obtained coating in example 5 and comparative example 2, and it can be seen from the combination of Table 2 and Table 3 that the PEDOT/PEI modified waterborne epoxy emulsion prepared by modifying the waterborne epoxy resin with the PEDOT/PEI is beneficial to improving the corrosion resistance and the dispersion stability of the coating. The technical scheme of the invention is advanced and feasible, and plays a leading demonstration role in the transformation and updating of the traditional anticorrosive paint product and the improvement of the product performance and value.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The anticorrosive paint is characterized in that the raw materials of the anticorrosive paint consist of a component A and a component B;
the component A is prepared from the following raw materials in parts by mass:
40-60 parts of poly (3, 4-ethylenedioxythiophene)/polyethyleneimine modified water-based epoxy emulsion,
0-10 parts of graphene dispersion liquid,
20-50 parts of filler,
1-4 parts of water-based auxiliary agent,
5-20 parts of water;
the component B is prepared from the following raw materials in parts by mass:
60-70 parts of water-based epoxy curing agent
The preparation method of the poly 3, 4-ethylenedioxythiophene/polyethyleneimine modified water-based epoxy emulsion comprises the following steps:
mixing a 3, 4-ethylenedioxythiophene monomer and a solvent, adding an initiator, and stirring for reaction to prepare a poly (3, 4-ethylenedioxythiophene) dispersion liquid;
mixing polyethyleneimine and waterborne epoxy resin, and stirring to prepare polyethyleneimine modified waterborne epoxy resin emulsion;
mixing the poly 3, 4-ethylenedioxythiophene dispersion liquid, the polyethyleneimine modified waterborne epoxy resin emulsion and an auxiliary agent, and shearing and emulsifying to prepare a poly 3, 4-ethylenedioxythiophene/polyethyleneimine modified waterborne epoxy emulsion;
the number average molecular weight of the polyethyleneimine is 600-10000;
the mass ratio of the polyethyleneimine to the waterborne epoxy resin is 1: (10-20).
2. The anticorrosive paint according to claim 1, wherein the solid content of the poly 3, 4-ethylenedioxythiophene/polyethyleneimine modified waterborne epoxy emulsion is 0.5-12%.
3. The anticorrosive paint according to any one of claims 1 to 2, wherein the mass ratio of the 3, 4-ethylenedioxythiophene to the solvent to the initiator is (1-4): (20-80): (1-2).
4. The anticorrosive paint according to any one of claims 1 to 2, wherein the stirring reaction time is 1 hour to 10 hours, and the stirring reaction temperature is 20 ℃ to 100 ℃; and/or
The initiator is selected from one or more of ammonium persulfate, sodium persulfate and potassium persulfate; and/or
The solvent is a mixture of alcohol and water, and the alcohol is selected from one of methanol, ethanol and propanol.
5. Anticorrosive coating according to any of claims 1 to 2, characterized in that the waterborne epoxy resin is selected from one or more of epoxy resins E-51, E-44, E-20, E-13 and E-12; and/or
The auxiliary agent comprises a defoaming agent and water.
6. The anticorrosive paint according to any one of claims 1 to 2, wherein the particle size of the poly 3, 4-ethylenedioxythiophene in the poly 3, 4-ethylenedioxythiophene dispersion is 30nm to 100 nm.
7. The anticorrosive paint according to claim 1, wherein the filler is selected from one or more of an anticorrosive pigment, a coloring pigment and an extender pigment;
the antirust pigment is selected from one or more of mica iron oxide ash, aluminum tripolyphosphate, zinc phosphate and zinc powder;
the coloring pigment is selected from one of permanent orange pigment and titanium dioxide;
the extender pigment is one or more selected from barium sulfate, mica powder, magnesium silicate hydrate, fumed silica and inorganic bentonite.
8. The anticorrosive paint according to claim 1, wherein the aqueous auxiliary agent is one or more selected from a wetting agent, a dispersing agent, a thixotropic agent, an anti-settling agent, an antifoaming agent, and a leveling agent.
9. The anticorrosive paint of claim 1, wherein the aqueous epoxy curing agent is one selected from polyamide, aliphatic amine, phenolic amine and polyether amine.
10. The anticorrosive coating according to any one of claims 1, 7, 8 and 9, wherein the mass ratio of the component A to the component B is (2-10): 1.
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| EP2028244A1 (en) * | 2007-08-02 | 2009-02-25 | Cytec Surface Specialties Austria GmbH | Water-borne paints based on epoxy resins |
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