Modified amine curing agent, preparation method, epoxy resin anticorrosive paint and application

Abstract

The invention provides a modified amine curing agent, a preparation method, epoxy resin anticorrosive paint and application, and belongs to the technical field of paint. The modified amine curing agent provided by the invention is prepared from preparation raw materials including alicyclic diamine, m-xylylenediamine, a first glycidyl ether reagent, a second glycidyl ether reagent and a glycidyl ester reagent through amination reaction, the alicyclic diamine contains at least one primary amine group; the first glycidyl ether reagent is ethylene glycol diglycidyl ether and / or bisphenol A type diglycidyl ether; and the second glycidyl ether reagent is 1, 4-butanediol diglycidyl ether and / or C12-14 glycidyl ether. The modified amine curing agent is combined with the curing characteristics of amide and phenolic aldehyde amine, the epoxy resin anticorrosive paint prepared from the modified amine curing agent has a proper curing speed, the adhesive force of a cured coating is high, the anticorrosive effect is good, and the epoxy resin anticorrosive paint is particularly suitable for a high-humidity environment and an underwater environment.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a modified amine curing agent and a preparation method thereof, and an epoxy resin anticorrosive coating and applications thereof. Background Art

[0002] With the continuous development of offshore oil, port terminals, wind power, hydropower and shipbuilding industries, many engineering structures in the marine environment, such as drilling and production equipment, drilling platforms, offshore oil and gas storage tanks, support frames of transmission pipelines, piers, steel piles, etc., have been immersed in seawater all year round, which has damaged the original anti-corrosion layer of the structure. When maintaining and protecting these structures, it is difficult to transfer them to land for maintenance and they can only be repaired in situ.

[0003] Epoxy resin coating is a coating formed by epoxy resin as a film-forming substance, compounded with certain fillers, additives, etc., which can form a coating with high adhesion and high corrosion resistance after curing. However, when using conventional epoxy resin coatings to protect the surface of substrate materials, it is usually suitable for environments with low humidity (relative humidity below 60%), and cannot adapt to high humidity environments and underwater environments. Summary of the invention

[0004] The purpose of the present invention is to provide a modified amine curing agent and a preparation method, an epoxy resin anti-corrosion coating and an application thereof. The epoxy resin anti-corrosion coating prepared by using the modified amine curing agent of the present invention has a suitable curing speed and a high adhesion of the coating after curing, and has a good anti-corrosion effect, and is particularly suitable for high humidity environments and underwater environments.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a modified amine curing agent, which is prepared by amination reaction of raw materials including alicyclic diamine, meta-xylylenediamine, a first glycidyl ether reagent, a second glycidyl ether reagent and a glycidyl ester reagent;

[0007] The alicyclic diamine contains at least one primary amine group;

[0008] The first glycidyl ether reagent is ethylene glycol diglycidyl ether and / or bisphenol A diglycidyl ether;

[0009] The second glycidyl ether reagent is 1,4-butanediol diglycidyl ether and / or C12-14 glycidyl ether.

[0010] Preferably, the alicyclic diamine includes one or more of isophorone diamine, 1,2-diaminocyclohexane and 1,3-bis(aminomethyl)cyclohexane; the molar ratio of the alicyclic diamine to meta-xylylenediamine is 1:0.6-1.6;

[0011] The molar ratio of the alicyclic diamine to the first glycidyl ether reagent is 1:0.02-0.05.

[0012] Preferably, the glycidyl ester reagent includes tert-butyl glycidyl ester and / or dimer acid diglycidyl ester; the molar ratio of the glycidyl ester reagent to the second glycidyl ether reagent is 1:0.5-1.0; the ratio of the total amount of the glycidyl ester reagent and the second glycidyl ether reagent to the amount of the alicyclic diamine is 0.15-0.3:1.

[0013] The present invention provides a method for preparing the modified amine curing agent described in the above technical solution, comprising the following steps:

[0014] The alicyclic diamine, meta-xylylenediamine, the first glycidyl ether reagent, the second glycidyl ether reagent and the glycidyl ester reagent are mixed and subjected to an amination reaction to obtain the modified amine curing agent.

[0015] Preferably, the amination reaction is carried out at a temperature of 80 to 85° C. and for a time of 60 to 90 minutes.

[0016] The present invention provides an epoxy resin anticorrosive coating, comprising a separately packaged component A and a component B, wherein the mass ratio of the component A to the component B is 1:0.5-2;

[0017] The component A comprises the following components in parts by weight: 93-98 parts of liquid epoxy resin, 3-12 parts of reactive diluent, 10-15 parts of first filler, 9-13 parts of barium sulfate, and 1-2 parts of fumed silica;

[0018] The B component includes the following components in parts by mass: 55-65 parts of the modified amine curing agent described in the above technical solution or the modified amine curing agent prepared by the preparation method described in the above technical solution, 8-10 parts of the second filler, 30-35 parts of barium sulfate, and 1-2 parts of fumed silica;

[0019] The first filler and the second filler are independently selected from one or more of quartz powder, titanium dioxide, antimony dioxide and aluminum hydroxide.

[0020] Preferably, the liquid epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, linear phenolic epoxy resin and multifunctional epoxy resin; and the active diluent is a glycidyl ether active diluent.

[0021] Preferably, the glycidyl ether active diluent includes a monofunctional diluent and / or a bifunctional diluent;

[0022] The monofunctional diluent includes C12-14 glycidyl ether and / or benzyl glycidyl ether;

[0023] The bifunctional diluent includes one or more of 1,4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

[0024] The present invention provides the application of the epoxy resin anti-corrosion coating described in the above technical solution in the surface protection of metal components or concrete components.

[0025] Preferably, the application environment includes an underwater environment or a high humidity environment; the relative humidity of the high humidity environment is ≥80%.

[0026] The present invention provides a modified amine curing agent, which is prepared by amination reaction of raw materials including alicyclic diamine, m-phenylenediamine, a first glycidyl ether reagent, a second glycidyl ether reagent and a glycidyl ester reagent; the alicyclic diamine contains at least one primary amine group; the first glycidyl ether reagent is ethylene glycol diglycidyl ether and / or bisphenol A type diglycidyl ether; the second glycidyl ether reagent is 1,4-butanediol diglycidyl ether and / or C12-14 glycidyl ether. The modified amine curing agent in the present invention combines the curing properties of amide and phenolic amine, and the epoxy resin anticorrosive coating prepared by the modified amine curing agent has a suitable curing speed, and the coating has high adhesion after curing and good anticorrosion effect, and is particularly suitable for high humidity environment and underwater environment. DETAILED DESCRIPTION

[0027] The present invention provides a modified amine curing agent, which is prepared by amination reaction of raw materials including alicyclic diamine, meta-xylylenediamine, a first glycidyl ether reagent, a second glycidyl ether reagent and a glycidyl ester reagent;

[0028] The alicyclic diamine contains at least one primary amine group;

[0029] The first glycidyl ether reagent is ethylene glycol diglycidyl ether and / or bisphenol A diglycidyl ether;

[0030] The second glycidyl ether reagent is 1,4-butanediol diglycidyl ether and / or C12-14 glycidyl ether.

[0031] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known to those skilled in the art or are prepared by methods well known to those skilled in the art.

[0032] The raw materials for preparing the modified amine curing agent of the present invention include alicyclic diamines, and the alicyclic diamines contain at least one primary amine group; as an embodiment of the present invention, the alicyclic diamines may include one or more of isophorone diamine, 1,2-diaminocyclohexane and 1,3-bis(aminomethyl)cyclohexane, specifically isophorone diamine, 1,2-diaminocyclohexane or 1,3-bis(aminomethyl)cyclohexane. In the embodiment of the present invention, the modified amine curing agent is prepared by using the above-mentioned alicyclic diamines, and the epoxy resin anticorrosive coating is further prepared by using the alicyclic diamines, which can increase the proportion of alicyclic structures inside the coating, and the alicyclic skeleton directly acts on the inside of the epoxy resin as a group structure, which is beneficial to improve the heat resistance of the coating, the mechanical strength under high temperature conditions, the weather resistance and the electrical insulation, and make the coating have better hue and transparency.

[0033] The raw materials for preparing the modified amine curing agent of the present invention include meta-xylylenediamine, and the molar ratio of the alicyclic diamine to the meta-xylylenediamine can be 1:0.6-1.6, specifically 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5 or 1:1.6. The present invention adopts meta-xylylenediamine to prepare the modified amine curing agent, which can form a ternary amine-based curing system through a condensation reaction, and further prepares epoxy resin anticorrosive coatings using the modified amine curing agent, which is beneficial to improving the heat resistance and corrosion resistance of the coatings, and due to the presence of a large number of aromatic rings, the coatings have better mechanical properties.

[0034] The raw materials for preparing the modified amine curing agent of the present invention include a first glycidyl ether reagent, wherein the first glycidyl ether reagent is ethylene glycol diglycidyl ether and / or bisphenol A diglycidyl ether, specifically ethylene glycol diglycidyl ether or bisphenol A diglycidyl ether; the molar ratio of the alicyclic diamine to the first glycidyl ether reagent can be 1:0.02-0.05, specifically 1:0.02, 1:0.03, 1:0.04 or 1:0.05. In the embodiment of the present invention, the first glycidyl ether reagent of the above type is used to reduce the viscosity of the curing system, which is beneficial to improve the film-forming effect of the coating, has no adverse effect on the performance of the coating after curing, and can also play a toughening role.

[0035] The raw materials for preparing the modified amine curing agent of the present invention include a second glycidyl ether reagent, and the second glycidyl ether reagent is 1,4-butanediol diglycidyl ether and / or C12-14 glycidyl ether, specifically 1,4-butanediol diglycidyl ether or C12-14 glycidyl ether. In the embodiment of the present invention, the second glycidyl ether reagent of the above type is used to reduce the viscosity of the curing system, and no VOC is generated during the reaction process. At the same time, the presence of a long fatty chain structure is conducive to improving the impact resistance and low-temperature operability of the cured coating.

[0036] The raw materials for preparing the modified amine curing agent of the present invention include glycidyl ester reagents; as an embodiment of the present invention, the glycidyl ester reagents may include tert-butyl glycidyl carbonate and / or dimer acid diglycidyl ester, specifically tert-butyl glycidyl carbonate or dimer acid diglycidyl ester. In the embodiment of the present invention, the modified amine curing agent is prepared by using the above-mentioned glycidyl ester reagents, which can introduce strong polar groups into the reaction system, which is beneficial to improve the adhesion of the entire coating after curing.

[0037] As an embodiment of the present invention, the molar ratio of the glycidyl ester reagent to the second glycidyl ether reagent can be 1:0.5-1.0, specifically 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1.0; the ratio of the total amount of the glycidyl ester reagent and the second glycidyl ether reagent to the amount of the alicyclic diamine can be 0.15-0.3:1, specifically 0.15:1, 0.17:1, 0.2:1, 0.22:1, 0.25:1, 0.28:1 or 0.3:1.

[0038] The present invention provides a method for preparing the modified amine curing agent described in the above technical solution, comprising the following steps:

[0039] The alicyclic diamine, meta-xylylenediamine, the first glycidyl ether reagent, the second glycidyl ether reagent and the glycidyl ester reagent are mixed and subjected to an amination reaction to obtain the modified amine curing agent.

[0040] As an embodiment of the present invention, the mixing may include: mixing alicyclic diamine and meta-xylylenediamine to obtain a mixed amine material; mixing the mixed amine material with a first glycidyl ether reagent and stirring evenly at 50-60°C; then dripping a mixed reagent of a second glycidyl ether reagent and a glycidyl ester reagent into the obtained mixed material to obtain a mixed reaction liquid. As an embodiment of the present invention, the amine value of the mixed amine material may be 550-650 mgKOH / g, further may be 590-620 mg KOH / g, and specifically may be 605 mg KOH / g. As an embodiment of the present invention, the dripping time may be 60-90 min, specifically may be 60 min, 70 min, 80 min or 90 min.

[0041] After obtaining the mixed reaction liquid, the present invention heats up to carry out the amination reaction. As an embodiment of the present invention, the temperature of the amination reaction can be 80-85°C, specifically 80°C, 81°C, 82°C, 83°C, 84°C or 85°C; the time can be 60-90min, specifically 60min, 70min, 80min or 90min; the amination reaction can be carried out in a protective atmosphere, and the protective atmosphere can be nitrogen; the amination reaction can be carried out under stirring conditions. As an embodiment of the present invention, during the amination reaction, the amine value of the system is measured once every 0.5h, and the amine value is stabilized at 300-350mg KOH / g at the end of the reaction, and can further be 310-320mg KOH / g; during the amination reaction, hydrogen and epoxy groups on the primary amines in the alicyclic diamine and metaphenylenediamine (the epoxy groups come from the first glycidyl ether reagent, the second glycidyl ether reagent and the glycidyl ester reagent) undergo an amination reaction to generate secondary amines, and the amination reaction process is a process in which the amine value decreases and tends to be stable. In the embodiment of the present invention, taking the alicyclic diamine as isophorone diamine and the epoxy group as the first glycidyl ether reagent (specifically ethylene glycol diglycidyl ether) as an example, the reaction formula involved in the amination reaction is as follows:

[0042]

[0043] As an embodiment of the present invention, after the amination reaction, it is preferred to further include subjecting the obtained amination product liquid to reduced pressure distillation; the conditions of the reduced pressure distillation include: the pressure can be 0.7-0.1 atmosphere, specifically 0.7 atmosphere, 0.8 atmosphere, 0.9 atmosphere or 0.1 atmosphere; the temperature can be 120-150° C., further can be 130-148° C., specifically can be 140-145° C.; the time can be 30-90 min, specifically can be 30 min, 40 min, 50 min, 60 min, 70 min, 80 min or 90 min.

[0044] As an embodiment of the present invention, the modified amine curing agent prepared by the above method has an appearance of a yellow transparent viscous liquid; the viscosity can be 2500-4000 mPa·s, specifically 3096 mPa·s; the amine value can be 300-350 KOH / g, specifically 310 mg KOH / g; the active hydrogen equivalent can be 105-120 wt(H), specifically 115 wt(H).

[0045] The present invention provides an epoxy resin anticorrosive coating, comprising a separately packaged component A and a component B, wherein the mass ratio of the component A to the component B is 1:0.5-2;

[0046] The component A comprises the following components in parts by weight: 93-98 parts of liquid epoxy resin, 3-12 parts of reactive diluent, 10-15 parts of first filler, 9-13 parts of barium sulfate, and 1-2 parts of fumed silica;

[0047] The B component includes the following components in parts by mass: 55-65 parts of the modified amine curing agent described in the above technical solution or the modified amine curing agent prepared by the preparation method described in the above technical solution, 8-10 parts of the second filler, 30-35 parts of barium sulfate, and 1-2 parts of fumed silica;

[0048] The first filler and the second filler are independently selected from one or more of quartz powder, titanium dioxide, antimony dioxide and aluminum hydroxide.

[0049] The epoxy resin anticorrosive coating of the present invention comprises separately packaged component A and component B, wherein the mass ratio of component A to component B is 1:0.5-2, further can be 1:0.8-1.2, and specifically can be 1:1. Component A and component B are described in detail below.

[0050] According to the mass fraction, the A component of the present invention includes 93 to 98 parts of liquid epoxy resin, specifically 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts or 99 parts. As an embodiment of the present invention, the liquid epoxy resin may include one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, linear phenolic epoxy resin and multifunctional epoxy resin, specifically bisphenol A epoxy resin (purchased from Jiangsu Yangnong Chemical Group Co., Ltd.), bisphenol F epoxy resin (purchased from Nanya Technology Co., Ltd.), linear phenolic epoxy resin (purchased from Nanya Technology Co., Ltd.) or multifunctional epoxy resin (purchased from Huntsman Chemical Co., Ltd.). The present invention uses liquid epoxy resin as a matrix material, which contains a large number of polar groups, and it is easier to replace the moisture on the surface of the coated material. During curing, it is mainly based on the epoxy ring-opening reaction, which has little effect on the main chain, and the curing shrinkage is low; at the same time, epoxy resin is suitable for preparing thick coatings with high solid content or solvent-free system, and has excellent anti-corrosion performance.

[0051] Based on the mass fraction of the liquid epoxy resin, the component A of the present invention includes 3 to 12 parts of active diluent, specifically 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts or 12 parts. As an embodiment of the present invention, the active diluent is a glycidyl ether active diluent; the glycidyl ether active diluent may include one or more of C12-14 glycidyl ether, 1,4-butanediol diglycidyl ether, benzyl glycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether, specifically C12-14 glycidyl ether (purchased from Anhui Huangshan Xinyuan Chemical Co., Ltd.), 1,4-butanediol diglycidyl ether, benzyl glycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether. The present invention uses active diluents to reduce viscosity, improve operability when mixing component A and component B, and viscosity during construction, and the use of active diluents facilitates the introduction of more fillers. When an inactive diluent is used, the coating is prone to blistering, which leads to the infiltration of bacteria or corrosive liquids, affecting the long-term protection of the coating; the above-mentioned type of active diluents used in the embodiments of the present invention have excellent hydrophobic properties, and the coating is not prone to blistering.

[0052] Based on the mass fraction of the liquid epoxy resin, the A component of the present invention includes 10 to 15 parts of the first filler, specifically 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts. As an embodiment of the present invention, the first filler can be selected from one or more of quartz powder, titanium dioxide, antimony dioxide and aluminum hydroxide, specifically quartz powder (purchased from Henan Luoyang Zhongyuan Chemical Co., Ltd.), titanium dioxide, antimony dioxide or aluminum hydroxide; the particle size of the first filler can be 1000 mesh. The use of the above-mentioned type of first filler in the embodiment of the present invention can make the coating have better gloss and higher hardness, and the coating has higher whiteness, which will not affect the coloring effect of different types of products.

[0053] Based on the mass fraction of the liquid epoxy resin, the component A of the present invention includes 9 to 13 parts of barium sulfate, specifically 9 parts, 10 parts, 11 parts, 12 parts or 13 parts. As an embodiment of the present invention, the particle size of the barium sulfate (purchased from Henan Luoyang Zhongyuan Chemical Co., Ltd.) can be 1000 mesh. The present invention uses barium sulfate as a filler, which has a large specific gravity and is used in combination with the first filler, which is conducive to increasing the thickness of the coating and making the coating have better wear resistance, water resistance, heat resistance, surface hardness and impact resistance.

[0054] Based on the mass fraction of the liquid epoxy resin, the component A of the present invention includes 1 to 2 parts of fumed silica, specifically 1 part, 1.3 parts, 1.5 parts, 1.7 parts or 2 parts. As an embodiment of the present invention, the fumed silica is purchased from Evonik Specialty Chemicals (Shanghai) Co., Ltd., with a brand name of R202. The present invention uses fumed silica to improve the thixotropy of epoxy resin anticorrosive coatings.

[0055] As an embodiment of the present invention, the A component may further include a color paste or a pigment; the color paste may include a solvent color paste or a water-based color paste; the pigment may include or an organic pigment, the inorganic pigment may include an oxide pigment, a chromate pigment or a metal pigment, and the organic pigment may include an azo pigment, a phthalocyanine pigment or an aromatic methane pigment. As an embodiment of the present invention, the content of the color paste in the A component may be 2-5wt%, and the content of the pigment in the A component may be 2-5wt%.

[0056] As an embodiment of the present invention, according to actual needs, the component A may also include an auxiliary agent to further adjust the applicability of the epoxy resin anti-corrosion coating; the auxiliary agent may include one or more of a film-forming aid, a wetting agent, a dispersant, a defoaming agent, a plasticizer, a thickener, an antifreeze agent, a leveling agent, a mildew inhibitor, a preservative and a pH adjuster.

[0057] In terms of mass fraction, the B component of the present invention comprises 55 to 65 parts of the modified amine curing agent of the above technical solution, and specifically can be 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts or 65 parts. The modified amine curing agent of the present invention can ensure that the epoxy resin anticorrosive coating has a suitable curing speed, and the adhesion can also meet the requirements. If alicyclic amines or fatty amines are used as curing agents, the curing time is short, but the underwater adhesion is low, and the coating has low strength in water; ketimine curing agents (made by condensation reaction of ketone compounds such as methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and polyamine compounds such as diethylenetriamine, m-phenylenediamine, m-phenylenediamine, and 1,3-bis(aminomethyl)cyclohexane) decompose in water to obtain primary amines, which are generally used for thin-coated products, and thick coatings (such as 50 to 200 μm thick) are difficult to hydrolyze internally; amide curing agents have good adhesion in humid environments, but the coating curing speed is too slow, affecting the construction period; the curing speed of phenolic amine curing agents is too fast, and the operation time cannot be controlled. In the present invention, the modified amine curing agent combines the curing characteristics of amides and phenolic amines, and both the curing speed and adhesion can meet the requirements, and it is also highly competitive from a cost perspective.

[0058] Based on the mass fraction of the modified amine curing agent, the B component of the present invention includes 8 to 10 parts of the second filler, specifically 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts. As an embodiment of the present invention, the second filler can be selected from one or more of quartz powder, titanium dioxide, antimony dioxide and aluminum hydroxide, specifically quartz powder, titanium dioxide, antimony dioxide or aluminum hydroxide; the particle size of the second filler can be 1000 mesh; in the embodiment of the present invention, the second filler can be the same type as the first filler.

[0059] Based on the mass fraction of the modified amine curing agent, the component B of the present invention includes 30 to 35 parts of barium sulfate, specifically 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts.

[0060] Based on the mass fraction of the modified amine curing agent, the component B of the present invention includes 1 to 2 parts of fumed silica, specifically 1 part, 1.3 parts, 1.5 parts, 1.7 parts or 2 parts.

[0061] The epoxy resin anticorrosive coating of the present invention adopts a solvent-free system, and the solid content of the system reaches more than 98wt%; wherein the A component and the B component have good compatibility with the pigment, and after compounding the pigment, the appearance of the coating obtained after the epoxy resin anticorrosive coating is cured can be adjusted, so that the downstream can flexibly design the appearance scheme according to the on-site conditions. At the same time, the coating structure obtained after the epoxy resin anticorrosive coating of the present invention is cured is very strong, and has good wear resistance and impact resistance.

[0062] The present invention provides the application of the epoxy resin anticorrosion coating described in the above technical solution in the surface protection of metal components or concrete components. As an embodiment of the present invention, the metal component may be an iron component or a stainless steel component. As an embodiment of the present invention, the application environment may include an underwater environment or a high humidity environment; the relative humidity of the high humidity environment may be ≥80%. The epoxy resin anticorrosion coating of the present invention can be operated in water or a high humidity environment, can be directly constructed and cured in an underwater or water environment, and is not affected by water interference. The adhesion, medium resistance and anticorrosion performance of the coating after curing can meet the requirements, shortening the construction period, saving a lot of manpower and material resources, and is suitable for marine anticorrosion, wharf anticorrosion, reservoir anticorrosion and oilfield underground anticorrosion, and can expand its application in various low temperature scenes (such as the epoxy resin anticorrosion coating of the present invention can be cured in a temperature environment of -10 to 5°C), further enhancing the market value of the product.

[0063] As an embodiment of the present invention, taking a metal component as an example, the application method of the epoxy resin anti-corrosion coating in an underwater environment may include the following steps:

[0064] Pre-treating the surface of a metal component (such as an iron sheet), specifically, removing rust or adhesive substances on the surface of the metal component by hand or by a manual machine (such as a spatula, an iron brush or an electric tool, etc.) to obtain a metal component with a clean and rough surface;

[0065] Prepare epoxy resin anti-corrosion coating, the epoxy resin anti-corrosion coating is prepared on-the-go, specifically, the component A and the component B of the epoxy resin anti-corrosion coating are mixed in an atmospheric environment according to a predetermined mass ratio, and the construction needs to be carried out as soon as possible after stirring evenly;

[0066] Soak the pretreated metal components in water, and apply (such as scraping or brushing) the prepared epoxy resin anti-corrosion coating on the surface of the metal components. During the coating process, use the squeezing effect of a rubber scraper or a stiff brush to push away the surface debris and allow the epoxy resin anti-corrosion coating to adhere to the surface of the metal components; apply pressure repeatedly for 3 to 4 times, and make sure it is evenly scraped; try to apply in two coats and control the strength to minimize pinholes or defects during the coating process.

[0067] As an embodiment of the present invention, the epoxy resin anti-corrosion coating is applied to the surface of a metal component or a concrete component and forms a coating after curing; the thickness of the coating can be 50 to 200 μm, further can be 100 to 200 μm, and further can be 150 to 200 μm.

[0068] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0069] The particle size of the quartz powder used in the following examples and comparative examples is 1000 mesh, and the particle size of the barium sulfate is 1000 mesh.

[0070] Preparation Example 1

[0071] The preparation method of modified m-phenylenediamine is as follows:

[0072] Isophorone diamine and meta-phenylenediamine are mixed at a molar ratio of 1:1 to obtain a mixed amine material with an amine value of 605 mgKOH / g; the mixed amine material is mixed with ethylene glycol diglycidyl ether at a molar ratio of 1:0.03, and the mixed amine material is placed in a four-necked flask with stirring, nitrogen protection, a thermometer and a condenser, and stirred evenly at 55°C; tert-butyl glycidyl carbonate and C12-14 glycidyl ether are mixed at a molar ratio of 1:0.7, and the obtained mixed reagent is dripped into the four-necked flask, the molar ratio of the isophorone diamine to the mixed reagent is 1:0.22, the dripping time is 60 minutes, the temperature is raised to 80°C after the dripping is completed, and the reaction is carried out under heat preservation conditions. During the reaction, the amine value is measured once every 0.5 hours, and when the heat preservation is 60 minutes, the amine value is stabilized at 310 mg KOH / g, and the insulation is ended; then the obtained product system is subjected to reduced pressure distillation at 0.1 atmospheres and 140-145°C for 30 minutes to obtain a modified amine curing agent (recorded as modified meta-phenylenediamine).

[0073] The index parameters of the modified metaphenylenediamine are as follows:

[0074] The appearance is yellow transparent viscous liquid; the viscosity at 25°C is 3096mPa·s; the amine value is 310mg KOH / g; and the active hydrogen equivalent is 115wt(H).

[0075] Example 1

[0076] Component A: Heat 95g of bisphenol A epoxy resin to 70°C, add 6g of C12-14 glycidyl ether under stirring, then add a mixture of 12g of quartz powder and 12g of barium sulfate in 5 batches, stir evenly, then add 1.5g of fumed silica, stir evenly to obtain the component A;

[0077] Component B: add 10 g of quartz powder and 34 g of barium sulfate to 60 g of curing agent (modified m-phenylenediamine), stir evenly, then add 2 g of fumed silica, stir evenly to obtain the component B;

[0078] When in use, the component A and the component B are evenly stirred in a mass ratio of 1:1 to obtain a coating base material.

[0079] Example 2

[0080] Component A: 95 g of bisphenol A epoxy resin was heated to 70° C., 6 g of 1,4-butanediol diglycidyl ether was added under stirring, and then a mixture of 12 g of quartz powder and 12 g of barium sulfate was added in 5 batches. After stirring evenly, 1.5 g of fumed silica was added and stirred evenly to obtain the component A;

[0081] Component B: add 10 g of quartz powder and 34 g of barium sulfate to 60 g of curing agent (modified m-phenylenediamine), stir evenly, then add 2 g of fumed silica, stir evenly to obtain the component B;

[0082] When in use, the component A and the component B are evenly stirred in a mass ratio of 1:1 to obtain a coating base material.

[0083] Example 3

[0084] Component A: Heat 95 g of bisphenol A epoxy resin to 70° C., add 6 g of benzyl glycidyl ether under stirring, then add a mixture of 12 g of quartz powder and 12 g of barium sulfate in 5 batches, stir evenly, then add 1.5 g of fumed silica, stir evenly to obtain the component A;

[0085] Component B: add 10 g of quartz powder and 34 g of barium sulfate to 60 g of curing agent (modified m-phenylenediamine), stir evenly, then add 2 g of fumed silica, stir evenly to obtain the component B;

[0086] When in use, the component A and the component B are evenly stirred in a mass ratio of 1:1 to obtain a coating base material.

[0087] Comparative Example 1

[0088] Component A: 95 g of bisphenol A epoxy resin was heated to 70° C., 6 g of benzyl alcohol was added under stirring, and then a mixture of 12 g of quartz powder and 12 g of barium sulfate was added in 5 batches. After stirring evenly, 1.5 g of fumed silica was added and stirred evenly to obtain the component A;

[0089] Component B: add 10 g of quartz powder and 34 g of barium sulfate to 60 g of curing agent (phenolic amine T31, purchased from Huangshan Tianhe Rubber Industry Co., Ltd.), stir evenly, then add 2 g of fumed silica, stir evenly to obtain the component B;

[0090] When in use, the component A and the component B are evenly stirred in a mass ratio of 1:1 to obtain a coating base material.

[0091] Comparative Example 2

[0092] Component A: Heat 95g of bisphenol A epoxy resin to 70°C, add 6g of C12-14 glycidyl ether under stirring, then add a mixture of 12g of quartz powder and 12g of barium sulfate in 5 batches, stir evenly, then add 1.5g of fumed silica, stir evenly to obtain the component A;

[0093] Component B: add 10 g of quartz powder and 34 g of barium sulfate to 60 g of curing agent (30 g of modified meta-phenylenediamine and 30 g of phenolic amine T31), stir evenly, then add 2 g of fumed silica, stir evenly to obtain the component B;

[0094] When in use, the component A and the component B are evenly stirred in a mass ratio of 1:1 to obtain a coating base material.

[0095] Comparative Example 3

[0096] Component A: Heat 95g of bisphenol A epoxy resin to 70°C, add 6g of C12-14 glycidyl ether under stirring, then add a mixture of 12g of quartz powder and 12g of barium sulfate in 5 batches, stir evenly, then add 1.5g of fumed silica, stir evenly to obtain the component A;

[0097] Component B: add 10 g of quartz powder and 34 g of barium sulfate to 60 g of curing agent (30 g of modified m-phenylenediamine and 30 g of polyamide 650, the polyamide 650 is purchased from Sanmu Chemical Co., Ltd.), stir evenly, then add 2 g of fumed silica, stir evenly to obtain the component B;

[0098] When in use, the component A and the component B are evenly stirred in a mass ratio of 1:1 to obtain a coating base material.

[0099] Comparative Example 4

[0100] Component A: Heat 95g of bisphenol A epoxy resin to 70°C, add 6g of C12-14 glycidyl ether under stirring, then add 24g of quartz powder in 5 batches, stir evenly, then add 1.5g of fumed silica, stir evenly to obtain the component A;

[0101] Component B: add 44 g of quartz powder to 60 g of curing agent (modified meta-xylylenediamine), stir evenly, then add 2 g of fumed silica, stir evenly to obtain the component B;

[0102] When in use, the component A and the component B are evenly stirred in a mass ratio of 1:1 to obtain a coating base material.

[0103] Comparative Example 5

[0104] Component A: Heat 95g of bisphenol A epoxy resin to 70°C, add 6g of C12-14 glycidyl ether under stirring, then add a mixture of 12g of quartz powder and 12g of barium sulfate in 5 batches, stir evenly, then add 1.5g of fumed silica, stir evenly to obtain the component A;

[0105] Component B: add 10 g of quartz powder and 34 g of barium sulfate to 60 g of curing agent (1,6-hexanediamine, abbreviated as HAD, purchased from Shanghai Lingfeng Chemical Reagent Co., Ltd.), stir evenly, then add 2 g of fumed silica, stir evenly to obtain the component B;

[0106] When in use, the component A and the component B are evenly stirred in a mass ratio of 1:1 to obtain a coating base material.

[0107] Test Example 1

[0108] The performance tests of the coating base materials in the embodiments and comparative examples are as follows:

[0109] Surface drying time and actual drying time: according to GB / T1728-1979 paint film and putty film drying time determination method;

[0110] Adhesion: Tested according to the GB / T5210-2006 paint and varnish pull-off adhesion test;

[0111] Flexibility: Tested according to GB / T1731-1993 paint film flexibility determination method;

[0112] Water resistance: tested according to GB / T1733-1993 paint film water resistance determination method;

[0113] Pull-off adhesion: According to GB / T5210-2006 paint film pull-off adhesion test;

[0114] Neutral salt spray resistance: According to GB / T1771-2007 neutral salt spray resistance;

[0115] Acid resistance: According to GB / T9274-1988 medium resistance test;

[0116] Alkali resistance: According to GB / T9274-1988 medium resistance test;

[0117] Impact resistance: According to GB1732-93 paint film impact resistance determination method;

[0118] Wear resistance: According to GB1768-89 paint film wear resistance test method;

[0119] Cathodic disbonding resistance: According to method B in GB / T7790-2008.

[0120] Tables 1 and 2 are the performance test results of the coating base materials in each embodiment and comparative example. It can be seen from Table 1 that the coating base material prepared by the embodiment of the present invention has excellent comprehensive performance. It can be seen from the comparison of Examples 1 to 3 that the coating base material obtained by using benzyl glycidyl ether as a diluent has the best effect. It can be seen from Table 2 that compared with Example 1, the effect of the coating base material obtained by using an inactive diluent in Comparative Example 1 is poor and easy to foam; in Comparative Examples 2 and 3, modified meta-phenylenediamine is compounded with phenolic amine T31 or polyamide 650, and the effect of the coating base material obtained is poor, easy to foam and fall off, and the operating time is short; in Comparative Example 4, only quartz powder is added, and the effect of the coating base material obtained is poor, easy to fall off, and the flexibility is poor, the wear resistance is poor, and the coating appearance shows that the flatness is lacking, and it has a better effect when paired with barium sulfate; 1,6-hexanediamine is used in Comparative Example 5, and the coating has poor wear resistance.

[0121] Table 1 Performance test results of coating base materials in the examples

[0122]

[0123] Table 2 Performance test results of coating base materials in comparative examples

[0124]

[0125]

[0126] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A modified amine curing agent, characterized in that: The method is prepared by subjecting raw materials including alicyclic diamine, meta-xylylenediamine, a first glycidyl ether reagent, a second glycidyl ether reagent and a glycidyl ester reagent to an amination reaction; The alicyclic diamine contains at least one primary amine group; The first glycidyl ether reagent is ethylene glycol diglycidyl ether and / or bisphenol A diglycidyl ether; The second glycidyl ether reagent is 1,4-butanediol diglycidyl ether and / or C12-14 glycidyl ether.

2. The modified amine curing agent according to claim 1, characterized in that The alicyclic diamine includes one or more of isophorone diamine, 1,2-diaminocyclohexane and 1,3-bis(aminomethyl)cyclohexane; the molar ratio of the alicyclic diamine to meta-xylylenediamine is 1:0.6-1.6; The molar ratio of the alicyclic diamine to the first glycidyl ether reagent is 1:0.02-0.

05.

3. The modified amine curing agent according to claim 1, characterized in that The glycidyl ester reagent includes tert-butyl glycidyl ester and / or dimer acid diglycidyl ester; the molar ratio of the glycidyl ester reagent to the second glycidyl ether reagent is 1:0.5-1.0; the ratio of the total amount of the glycidyl ester reagent and the second glycidyl ether reagent to the amount of the alicyclic diamine is 0.15-0.3:

1.

4. The method for preparing the modified amine curing agent according to any one of claims 1 to 3, characterized in that: The following steps are involved: The alicyclic diamine, meta-xylylenediamine, the first glycidyl ether reagent, the second glycidyl ether reagent and the glycidyl ester reagent are mixed and subjected to an amination reaction to obtain the modified amine curing agent.

5. The preparation method according to claim 4, characterized in that: The temperature of the amination reaction is 80-85° C. and the time is 60-90 minutes.

6. An epoxy resin anticorrosive coating, characterized in that: The method comprises a subpackaged component A and a component B, wherein the mass ratio of the component A to the component B is 1:0.5-2; The component A comprises the following components in parts by weight: 93-98 parts of liquid epoxy resin, 3-12 parts of reactive diluent, 10-15 parts of first filler, 9-13 parts of barium sulfate, and 1-2 parts of fumed silica; The B component includes the following components in parts by mass: 55-65 parts of the modified amine curing agent according to any one of claims 1 to 3 or the modified amine curing agent prepared by the preparation method according to claim 4 or 5, 8-10 parts of the second filler, 30-35 parts of barium sulfate, and 1-2 parts of fumed silica; The first filler and the second filler are independently selected from one or more of quartz powder, titanium dioxide, antimony dioxide and aluminum hydroxide.

7. The epoxy resin anticorrosive coating according to claim 6, characterized in that: The liquid epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, linear phenolic epoxy resin and multifunctional epoxy resin; the active diluent is a glycidyl ether active diluent.

8. The epoxy resin anticorrosive coating according to claim 7, characterized in that: The glycidyl ether active diluent includes a monofunctional diluent and / or a bifunctional diluent; The monofunctional diluent includes C12-14 glycidyl ether and / or benzyl glycidyl ether; The bifunctional diluent includes one or more of 1,4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

9. Use of the epoxy resin anticorrosive coating according to any one of claims 6 to 8 in the surface protection of metal components or concrete components.

10. The use according to claim 9, characterized in that: The application environment includes an underwater environment or a high humidity environment; the relative humidity of the high humidity environment is ≥80%.

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