Addition amine curing agent capable of being used for underwater curing, coating composition of addition amine curing agent and application of addition amine curing agent

Abstract

The invention provides an addition amine curing agent capable of being used for underwater curing and a coating composition and application of the addition amine curing agent. The coating composition comprises a first component and a second component, the first component comprises epoxy resin, a reactive diluent and filler, the second component comprises a curing agent and a non-reactive diluent, and the curing agent comprises a chlorosulfonated polyethylene addition amine curing agent formed by addition of chlorosulfonated polyethylene and diamine. A coating layer formed by the coating contains long-chain high-molecular chlorosulfonated polyethylene, a self-plasticized rubber phase is formed, the self-plasticized rubber phase has impact resistance of bearing water flow scouring, and chlorosulfo groups can react with water to realize an underwater curing function. The coating does not contain a solvent, the one-time coating thickness can reach 5000 microns, and rapid and efficient underwater coating is achieved. The coating is suitable for maintenance and coating of underwater robots, the adhesive force of a coating cured in water reaches 16.8 MPa, and the coating is good in flexibility, impact resistance and long-term corrosion resistance and suitable for corrosion protection of metal structural components operating in the marine environment.

Description

Technical Field

[0001] The present invention belongs to the technical field of anti-corrosion coatings, and particularly relates to an addition amine curing agent capable of underwater curing, and its coating composition and application. Background Art

[0002] The utilization of marine resources involves many fields, such as offshore wind power, marine photovoltaic, deep-sea aquaculture, deep-sea oil drilling platforms, coastal industrial facilities, and cross-sea bridges. During the operation of these marine equipment and devices, the erosion by seawater and marine organisms will cause the peeling and cracking of the original coatings on the equipment and devices, resulting in the rusting of metal structures. In this case, it is necessary to repair and recoat them. However, the marine environment is relatively harsh, such as marine winds and waves, seawater immersion, and the uncontrollability of marine climate, making the equipment repair and construction difficult. The surfaces of facilities in the splash zone and tidal zone of the ocean are covered with water dew due to high humidity. The adhesion of anti-corrosion coating materials applied in the atmospheric environment after curing on the wet surface is poor. And the repair and construction of underwater structural facilities of equipment are even more difficult because ordinary coatings generally cannot achieve construction and curing in water. In addition, the repaired coating has to withstand the scouring of sea waves and water currents, as well as the abrasion of seawater mixed with sand and stones. Therefore, the repaired coating is required to have high impact resistance, good wear resistance, and strong adhesion.

[0003] The industrial community has been constantly searching for solutions to underwater curable coating materials for many years. For example, the prior art CN1752162A discloses a marine heavy anti-corrosion coating and its preparation method, which prepares a coating that can be cured underwater by modifying liquid epoxy resin. Although the formed coating can be cured underwater, the construction thickness can only reach 100 - 500 μm at a time, and multiple constructions are required to reach the film thickness, and the surface treatment needs to reach the GB8923 St3 level. The prior art CN108192471A improves the flexibility and impact resistance of the coating by physically blending and introducing polysulfide rubber and petroleum resin. However, the polysulfide rubber exists in a particulate state in the coating, which leads to the problem of phase separation during its application, thus affecting the anti-corrosion performance. The prior art CN104745046A discloses an underwater curable coating, which improves the water resistance and adhesion of the coating by modifying petroleum resin into an unsaturated polymer containing phenol. However, this petroleum resin is a non-reactive component and cannot become a part of the cured epoxy resin network. Therefore, the water resistance and impact resistance of the coating will decline during long-term use.

[0004] Coatings that can be used for the operation and maintenance of marine equipment need to have the function of curing underwater, provide long-term protection in highly corrosive environments, and can obtain a high film thickness with a single coating, be able to cure quickly, and also be resistant to water flow erosion, abrasion, and corrosion. Due to the safety issues of manual maintenance of underwater structures, underwater robots will increasingly replace the work of divers. Therefore, the demand for new coating compositions suitable for underwater robot repair coating is increasing day by day. It can be seen that providing a coating composition that can cure underwater is one of the problems that need to be solved urgently at present. Summary of the Invention

[0005] To solve all or part of the above technical problems, the present invention provides the following technical solutions:

[0006] One of the purposes of the present invention is to provide an addition amine curing agent that can be used for underwater curing, and the structure of the addition amine curing agent is shown in Formula I:

[0007]

[0008] Wherein, R1 is selected from an aliphatic group, an aromatic group or a polyether group, n1 is an integer between 1 and 1000, n2 is an integer between 1 and 1000, m1 is an integer between 1 and 100, and m2 is an integer between 1 and 100.

[0009] Another purpose of the present invention is to provide a preparation method of an addition amine curing agent that can be used for underwater curing, including: carrying out an addition reaction on a mixed reaction system containing chlorosulfonated polyethylene, diamine and an inert diluent to obtain a chlorosulfonated polyethylene addition amine curing agent.

[0010] In some embodiments, the structure of the chlorosulfonated polyethylene is shown in Formula II:

[0011]

[0012] Wherein, n1 is an integer between 1 and 1000, n2 is an integer between 1 and 1000, m1 is an integer between 1 and 100, and m2 is an integer between 1 and 100;

[0013] The reaction formula for the addition reaction of the chlorosulfonated polyethylene and the diamine is as follows:

[0014]

[0015] In some embodiments, the number average molecular weight of the chlorosulfonated polyethylene is 10,000 - 100,000.

[0016] In some embodiments, the diamine includes one or a combination of more of an aliphatic amine, an aromatic amine, a polyether amine, and an alicyclic amine.

[0017] Exemplarily, the aliphatic amine is, for example:

[0018]

[0019] The cycloaliphatic amine is, for example:

[0020]

[0021] The aromatic amine includes, for example, one or more of the following structures, but is not limited thereto:

[0022]

[0023] The polyetheramine includes, for example, one or more of the following structures, but is not limited thereto:

[0024]

[0025] wherein, n is 1 to 100.

[0026]

[0027] wherein, x is 1 to 100, y is 1 to 100, and z is 1 to 100.

[0028] In some embodiments, the non-reactive diluent includes a combination of one or more of dibutyl phthalate, benzyl alcohol, phenethyl alcohol, cashew shell oil polyol, and cardanol-based glycidyl ether.

[0029] In some embodiments, the reaction molar ratio of chlorosulfonated polyethylene to diamine in the mixed reaction system is 1:0.1 - 1.

[0030] In some embodiments, the temperature of the reaction is above 80°C, preferably 80 - 100°C

[0031] In some embodiments, the reaction time is 3 - 5 h.

[0032] In some embodiments, the preparation method of the addition amine curing agent specifically includes: first mixing chlorosulfonated polyethylene with the non-reactive diluent and heating to above 80°C, and then adding the diamine under stirring conditions and reacting for 3 - 5 h.

[0033] The third object of the present invention is to provide an addition amine curing agent that can be used for underwater curing, which is prepared by the method described in any one of the above.

[0034] The fourth object of the present invention is to provide the application of the addition amine curing agent that can be used for underwater curing in the preparation of a coating composition that can be cured underwater.

[0035] A fifth object of the present invention is to provide a coating composition that can be cured underwater, including a first component and a second component, and the mass ratio of the first component to the second component is 1:0.1 - 0.7;

[0036] Wherein, the first component includes 20 - 40wt% epoxy resin, 10 - 20wt% reactive diluent, and 30 - 60wt% filler;

[0037] The second component includes 50 - 70wt% curing agent and 5 - 30wt% non-reactive diluent, and the curing agent includes the above-mentioned addition amine curing agent.

[0038] The coating formed by reacting with the addition amine curing agent used in the present invention contains long-chain polymer chlorosulfonated polyethylene, forming a self-plasticizing rubber phase, so that the coating has good impact resistance and can withstand long-term scouring by water flow. And, the chlorosulfonyl group in the addition amine curing agent can react with water to consume the moisture on the surface of the underwater structure, realizing underwater curing. The reaction mechanism is as follows:

[0039]

[0040] The formed coating has good adhesion, the coating can be thick-filmed, will not cause solvent retention, and can reach a thickness of 5000 microns in one coating, saving construction time and improving construction efficiency.

[0041] In addition, the coating composition provided by the present invention uses a reactive diluent and an epoxy resin system. The reactive diluent can not only replace volatile solvents, but also react with the epoxy resin to become a part of the molecular structure, increasing the toughness of the paint film, so that the coating can maintain good stability and durability in a humid environment.

[0042] In some embodiments, the non-reactive diluent in the coating composition includes one or more combinations of dibutyl phthalate, benzyl alcohol, phenethyl alcohol, cashew shell oil polyol, and cardanol-based glycidyl ether.

[0043] In some embodiments, the epoxy resin includes one or a combination of two or more of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenolic epoxy resin, but is not limited thereto.

[0044] In some embodiments, the epoxy resin is a single or composite epoxy resin, and the composite epoxy resin includes bisphenol A epoxy resin and also includes bisphenol F epoxy resin or phenolic epoxy resin.

[0045] In some preferred embodiments, in the composite epoxy resin, bisphenol A epoxy resin and the above-mentioned other resins are mixed in a mass ratio of 1:0.1 - 1, for example, 1:0.2 - 0.8.

[0046] In some embodiments, the reactive diluent includes one or a combination of two or more of allyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, octyl glycidyl ether, isopropyl glycidyl ether, phenyl glycidyl ether, o-tolyl glycidyl ether, cardanol modified glycidyl ether, 1,4-butanediol diglycidyl ether, propylene oxide butyl ether, cardanol glycidyl ether, etc., but not limited thereto.

[0047] In some embodiments, the filler includes any one or a combination of two or more of rutile titanium dioxide, aluminum clay, talc powder, silica powder, feldspar powder, mica powder, barite barium sulfate, etc., and is not limited thereto.

[0048] In some embodiments, the first component further includes 0.5-5 wt% of an auxiliary agent. The auxiliary agent includes, for example, one or a combination of more than one of a dispersant and a thixotropic agent, but is not limited thereto.

[0049] In some embodiments, the dispersant includes any one or a combination of two or more of YCK-1530, YCK-1560, YCK-1450, YCK-1480, BYK-9076, BYK-066, BYK-9077, etc., and is not limited thereto.

[0050] In some embodiments, the thixotropic agent includes any one or a combination of two or more of polyamide wax, polyethylene wax, fumed silica, organic bentonite, hydrogenated castor oil, etc., and is not limited thereto.

[0051] In some embodiments, the first component further includes a pigment.

[0052] In some embodiments, the preparation method of the coating component includes, for example: mixing the epoxy resin and the reactive diluent according to a mass ratio and stirring at a rotation speed of 500-1000 r / min, adding the filler while maintaining stirring, optionally adding one or more of a thixotropic agent, a dispersant, and a pigment, and then dispersing for more than 30 min at a high speed of 1000-2000 r / min to mix evenly to form a first component; uniformly mixing the first component and the second component according to a weight ratio of 1:0.1-0.7 to form the coating composition.

[0053] After the curing reaction of the composition of the present invention, the coating contains long-chain polymer chlorosulfonated polyethylene to form a self-plasticizing rubber phase, which has the performance of withstanding water flow scouring and impact resistance. Moreover, the chlorosulfonyl group can react with water to achieve the function of underwater curing. At the same time, the coating composition does not contain solvents, and the thickness of a single coating can reach 5000 microns, realizing rapid and efficient coating underwater, and is suitable for the scraping operation of underwater robots. The adhesion of the coating cured in water is as high as 16.8 MPa, with good flexibility, impact resistance, cathodic disbondment resistance and long-term corrosion resistance, and is suitable for the corrosion protection of metal structural components in the underwater, waterline or splash zone of marine environment operation. The coating composition of the present invention has the function of rapid underwater curing, is not restricted by the time of ebb and flow, shortens the operation and maintenance time, and solves the problem of underwater corrosion operation and maintenance of marine equipment.

[0054] The sixth object of the present invention is to provide the application of the coating composition in a protective coating, and the protective coating has at least an anti-corrosion function.

[0055] In some embodiments, the protective coating is a protective coating used for equipment in a high-humidity environment. The equipment in the high-humidity environment includes marine equipment. For example, facilities and equipment used in an environment close to water bodies (including oceans, rivers, lakes, groundwater, etc.) or in contact with water bodies, including marine oil and gas engineering facilities, marine wind power facilities, pile foundations of cross-sea bridges, marine steel pipe piles, offshore platforms and other marine equipment, also include underwater facilities used in water bodies such as rivers, as well as coastal equipment, port machinery, buried pipelines, and so on.

[0056] In some embodiments, the application includes: under the condition of contacting water, directly constructing the substrate with the coating composition to form a protective coating on the substrate or maintaining and repairing the damaged protective coating on the substrate.

[0057] The coating composition of the present invention is not only suitable for the anti-corrosion of new engineering structures, and because it can be directly constructed on a substrate with water on its surface and can be continuously cured in water, so the coating can also be directly constructed underwater, and is particularly suitable for on-site construction of facilities and equipment in a high-humidity environment, such as on-site maintenance of facilities and equipment operating in water bodies such as oceans and rivers. And a thick film coating with a thickness of 5000 microns can be obtained by a single construction, providing effective anti-corrosion for metal structural components in marine environment, industrial corrosion environment or buried ground, so as to ensure the stable and safe operation of the structural components during service.

[0058] A seventh object of the present invention is to provide a protective structure formed on the surface of a substrate for protecting the substrate. The protective structure includes a protective coating formed from the coating composition of the present invention. The protective coating formed from the coating composition of the present invention can be rapidly cured, has high adhesion, good workability, and excellent salt spray resistance and seawater immersion resistance.

[0059] In some embodiments, the thickness of the protective coating is 300 - 5000 μm.

[0060] In some embodiments, the substrate has a non-contact water area and / or a contact water area. The non-contact water area is an area where the substrate does not directly contact water under normal use conditions (such as the atmospheric area above water), and the contact water area is an area where the substrate directly contacts water under normal use conditions (such as the splash zone at the waterline and the submerged zone underwater); when the protective structure is provided in the non-contact water area of the substrate, the thickness of the corrosion protection coating is 300 - 1500 μm; when the protective structure is provided in the contact water area of the substrate, the thickness of the corrosion protection coating is 500 - 4000 μm.

[0061] In some preferred embodiments, when the protective structure is provided in the contact water area of the substrate, the thickness of the corrosion protection coating is 1000 - 3000 μm.

[0062] In some embodiments, the substrate includes a substrate for marine equipment.

[0063] An eighth object of the present invention is to provide a method for coating and preparing the protective structure, including coating the coating composition on the surface of the substrate by at least one of manual coating or robotic coating. The coating method includes one or a combination of spraying, brushing, roll coating, scraping, or spreading.

[0064] In some embodiments, in the non-contact water area of the substrate, the coating method uses at least one of spraying, brushing, or roll coating; in the contact water area of the substrate, the coating method uses at least one of roll coating, scraping, or spreading.

[0065] In some preferred embodiments, in the contact water area of the substrate, underwater robots are used to perform scraping and / or spreading.

[0066] Compared with the prior art, the present invention has at least the following beneficial effects:

[0067] (1) The coating composition of the present invention uses a curing agent formed by the addition reaction of chlorosulfonated polyethylene and diamine, so that the formed coating contains long-chain polymer chlorosulfonated polyethylene, forming a self-plasticizing rubber phase. Therefore, the coating has good impact resistance and can withstand the long-term impact of water flow. In addition, the chlorosulfonyl group in the curing agent can react with water, enabling the coating to be applied when there is moisture on the substrate surface, or directly underwater, achieving rapid underwater curing. Moreover, the coating obtained by construction in a water-containing environment also has good adhesion.

[0068] (2) The coating composition of the present invention uses a reactive diluent and an epoxy resin system. The reactive diluent therein not only replaces volatile solvents, but also can react with the epoxy resin to become a part of the molecular structure, increasing the toughness of the paint film and enabling the coating to maintain good stability and durability in a humid environment.

[0069] (3) Under the condition of the reactive diluent, the coating composition of the present invention does not need to use other volatile solvents. The coating composition has excellent thick-film coating properties. One-time coating can reach a thickness of 5000 microns, and it can be quickly and efficiently coated underwater, saving construction time and improving construction efficiency.

[0070] (4) The protective coating formed by using the coating composition of the present invention has high adhesion. The coating formed by construction in water can reach more than 16.8 MPa, with good flexibility and impact resistance, good workability, and excellent cathodic disbondment resistance, salt spray resistance, and seawater immersion resistance, and has good application prospects in the field of anti-corrosion.

[0071] (5) Based on the good workability and rapid underwater curing property of the coating composition in a high-humidity environment, it can be used to in-situ coat equipment directly in water, especially in a high-humidity environment, or to perform on-site maintenance on the equipment during operation. For example, it can be applied to the operation and maintenance of facilities and equipment in water bodies such as the ocean, rivers, and lakes, which can shorten the operation and maintenance time and solve the problem of underwater corrosion operation and maintenance of marine equipment. Description of the Drawings

[0072] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0073] Figure 1 It is a schematic diagram of on-site construction of a marine equipment using the coating composition in an embodiment of the present invention;

[0074] Figure 2 It is a photograph of sample preparation by water curing using the coating composition in an embodiment of the present invention;

[0075] Figure 3 It is a photograph of the corrosion resistance test of a steel pipe coated with the coating composition in seawater in an embodiment of the present invention;

[0076] Figure 4 It is a photograph of the adhesion test results of the coatings formed by the coating compositions in Comparative Examples 1-4 of the present invention.

[0077] Figure 5 It is a photograph of the adhesion test results of the coatings formed by the coating compositions in Examples 1-4 of the present invention. Detailed Description of Specific Embodiments

[0078] The technical solutions of the present invention will be described in detail below in conjunction with specific embodiments, so that those skilled in the art can better understand and implement the technical solutions of the present invention. The specific functional details disclosed herein should not be construed as restrictive, but only as the basis of the claims and as a representative basis for teaching those skilled in the art to adopt the present invention in different ways in any appropriate detailed embodiment.

[0079] The experimental materials used in the following examples and comparative examples can be obtained by conventional commercial channels or biochemical reagent companies without special instructions; the test methods, without special instructions, are all conventional methods.

[0080] Example 1

[0081] Mix 10 g of bisphenol A epoxy resin, 20 g of bisphenol F epoxy resin, and 10 g of Cardolite NC-513 reactive diluent, stir at a speed of 500 r / min to make them evenly mixed, then add 2 g of thixotropic agent polyamide wax, and stir at a speed of 1000 r / min for 10 min. Then add 1 g of dispersant BYK-9076 and 60 g of mixed filler (the mixed filler consists of 30 g of silica powder, 15 g of talc powder, and 15 g of barite), and stir at a speed of 1200 r / min and a temperature of 60 °C for 30 min to form the first component.

[0082] Evenly mix 40 g of chlorosulfonated polyethylene CSM2910 (molecular weight 30000) with 30 g of dibutyl phthalate non-reactive diluent, heat to 80 °C for dissolution and stir evenly, add 30 g of m-phenylenediamine while maintaining a stirring speed of 500 r / min, and react at the above temperature and speed for 3 hours to form the second component. The content of chlorosulfonated polyethylene addition amine curing agent in the second component is 70 wt%, and the content of dibutyl phthalate non-reactive diluent is 30 wt%.

[0083] Mix the prepared first component and the second component evenly according to a weight ratio of 1:0.1 to form an underwater-curable maintenance coating, and then coat and prepare samples for plate testing.

[0084] Use the coating composition of this example to prepare samples for curing in water: First, place the test steel plate or steel pipe pile (the surface of the unrusted steel pipe pile is as shown in a of Figure 2 ) in a salt spray chamber with 5% NaCl for 7 days to make it rust until it reaches a D-level rusting degree according to GB / T8923, and the rust thickness > 2000 μm (as shown in b of Figure 2 ); then manually grind and remove rust to St 2 level, and then place the surface-ground test steel plate or steel pipe in seawater, and brush the coating prepared in this example on it (as shown in c of Figure 2 ). Then place the steel pipe coated with the coating in seawater for corrosion resistance testing, as shown in Figure 3 .

[0085] Test the adhesion of the coating formed by the coating composition of this example: Brush a 300-micron-thick coating on the surface of a test steel plate (size 150x70x3 mm), then soak it in seawater for 30 days, and test the adhesion of the coating according to the pull-off method of GB / T5210-2006. The adhesion test results are as shown in Figure 5 .

[0086] Example 2

[0087] Mix 30 g of bisphenol A epoxy resin and 10 g of tert-butyl glycidyl ether active diluent, stir at a speed of 500 r / min to mix them evenly, then add 2 g of thixotropic agent polyamide wax, and stir for 10 min at a speed of 1000 r / min. Then add 1 g of dispersant BYK-9076 and 30 g of mixed filler (the mixed filler consists of 10 g of silica powder, 10 g of talc powder, and 10 g of barite barium sulfate), and stir at a speed of 1200 r / min and a temperature of 60 °C for 30 min to form the first component.

[0088] Mix 25 g of chlorosulfonated polyethylene CSM4010 (molecular weight 40000) and 30 g of benzyl alcohol non-active diluent evenly, heat to 80 °C for dissolution and stir evenly, add 45 g of diethylenetriamine while maintaining a stirring speed of 500 r / min, and react at the above temperature and speed for 3 hours to form the second component. The content of chlorosulfonated polyethylene addition amine curing agent in the second component is 50 wt%, and the content of benzyl alcohol non-active diluent is 50 wt%.

[0089] Mix the prepared first component and the second component evenly at a weight ratio of 1:0.3 to form an underwater-curable maintenance coating, and then coat and prepare samples for plate testing.

[0090] Use the same method as in Example 1 to test the underwater curing performance, corrosion resistance, and adhesion of the coating composition. The test results are shown in Table 1.

[0091] Example 3

[0092] Mix 30 g of bisphenol A epoxy resin and 10 g of cardanol-modified glycidyl ether active diluent, stir at a speed of 500 r / min to make them mix evenly, then add 2 g of thixotropic agent polyamide wax, and stir at a speed of 1000 r / min for 10 min. Then add 1 g of dispersant BYK-9076 and 57 g of mixed filler (the mixed filler consists of 27 g of silica powder, 15 g of talc powder, and 15 g of barite barium sulfate), and stir at a speed of 1200 r / min and a temperature of 60 °C for 30 min to form the first component;

[0093] Mix 20 g of chlorosulfonated polyethylene CSM2305 (molecular weight 100000) and 30 g of phenethyl alcohol non-active diluent evenly, heat to 80 °C for dissolution and stir evenly, add 50 g of polyetheramine D230 while maintaining a stirring speed of 500 r / min, and react at the above temperature and speed for 3 hours to form the second component. The content of chlorosulfonated polyethylene addition amine curing agent in the second component is 70 wt%, and the content of phenethyl alcohol non-active diluent is 30 wt%.

[0094] Mix the prepared first component and the second component evenly at a weight ratio of 1:0.5 to form an underwater-curable maintenance coating, and then coat and prepare samples for plate testing.

[0095] Use the same method as in Example 1 to test the underwater curing performance, corrosion resistance, and adhesion of the coating composition. The test results are shown in Table 1.

[0096] Example 4

[0097] Mix 30 g of bisphenol A epoxy resin and 10 g of cardanol-modified glycidyl ether active diluent, stir at a speed of 500 r / min to make them mix evenly, then add 2 g of thixotropic agent polyamide wax, and stir at a speed of 1000 r / min for 10 min. Then add 1 g of dispersant BYK-9076 and 57 g of mixed filler (the mixed filler consists of 27 g of silica powder, 15 g of talc powder, and 15 g of barite barium sulfate), and stir at a speed of 1200 r / min and a temperature of 60 °C for 30 min to form the first component.

[0098] 35 g of chlorosulfonated polyethylene CSM2305 (molecular weight 100,000) was uniformly mixed with 30 g of phenethyl alcohol non-reactive diluent, heated to 80 °C for dissolution and stirring until uniform. Under the condition of maintaining a stirring speed of 500 r / min, 35 g of alicyclic amine 1,3-cyclohexanedimethanamine was added, and the reaction was carried out for 3 hours while maintaining the above temperature and rotation speed to form the second component. Among them, the content of chlorosulfonated polyethylene addition amine curing agent in the second component was 70 wt%, and the content of phenethyl alcohol non-reactive diluent was 30 wt%.

[0099] The prepared first component and the second component were mixed uniformly according to a weight ratio of 1:0.7 to form an underwater-curable maintenance coating, and then the prepared sample was coated for plate testing.

[0100] The same method as in Example 1 was used to test the underwater curing performance, corrosion resistance and adhesion of the coating composition, and the test results are shown in Table 1.

[0101] Comparative Example 1:

[0102] Comparative Example 1 was basically the same as Example 1, except that: all 40 g of chlorosulfonated polyethylene CSM2910 in the second component of Example 1 was replaced with m-phenylenediamine, and the rest was carried out in the same manner as in Example 1.

[0103] The same method as in Example 1 was used to test the underwater curing performance, corrosion resistance and adhesion of the coating composition, and the test results are shown in Table 1.

[0104] Comparative Example 2:

[0105] Comparative Example 2 was basically the same as Example 2, except that: all 25 g of chlorosulfonated polyethylene CSM4010 (molecular weight 40,000) in the second component of Example 2 was replaced with diethylenetriamine, and the rest was carried out in the same manner as in Example 2.

[0106] The same method as in Example 1 was used to test the underwater curing performance, corrosion resistance and adhesion of the coating composition, and the test results are shown in Table 1.

[0107] Comparative Example 3:

[0108] Comparative Example 3 was basically the same as Example 3, except that: all 20 g of chlorosulfonated polyethylene CSM2305 (molecular weight 100,000) in the second component of Example 3 was replaced with polyetheramine D230, and the rest was carried out in the same manner as in Example 1.

[0109] The same method as in Example 1 was used to test the underwater curing performance, corrosion resistance and adhesion of the coating composition, and the test results are shown in Table 1.

[0110] Comparative Example 4

[0111] Comparative Example 4 was basically the same as Example 1, except that in Comparative Example 4, all 35 g of chlorosulfonated polyethylene CSM2305 (molecular weight 100,000) was replaced with alicyclic amine 1,3-cyclohexanediamine, and the rest was the same as in Example 4.

[0112] The water curing performance, corrosion resistance and adhesion of the coating composition were tested by the same method as in Example 1, and the test results are shown in Table 1.

[0113] Figure 4 It is a photo of the adhesion test results of the coatings formed by the coating compositions in Comparative Examples 1-4.

[0114] Table 1 Characterization results of the properties of the coatings prepared in Comparative Examples 1-3 and Examples 1-3

[0115]

[0116] As can be seen from Table 1, the coatings in Examples 1-4 can be rapidly cured underwater, the impact resistance of the coatings is higher than the highest index of 50 Kgf.cm in the standard range of GB / T 1732-2020, and the adhesion of the coatings formed by underwater curing is significantly higher than the highest 16.8 MPa sample plate in the comparative examples, showing excellent performance compared with Comparative Examples 1-4.

[0117] It can be seen that the coating provided by the present invention can achieve rapid curing in water, has excellent impact resistance and adhesion of the coating, and has a long corrosion resistance time. Therefore, as Figure 1 shown, the coating composition provided by the present invention is suitable for the anti-corrosion of equipment and facilities in high-humidity environments. Based on its ability to rapidly cure on a matrix in contact with water, it can be used for underwater construction, and is particularly suitable for on-site operation, repair and maintenance of marine equipment.

[0118] All aspects, embodiments, features and examples of the present invention should be considered illustrative in all respects and are not intended to limit the present invention, the scope of which is only defined by the claims. Without departing from the spirit and scope of the claimed invention, those skilled in the art will appreciate other embodiments, modifications and uses.

[0119] In addition, the inventors of this case also referred to the foregoing embodiments and conducted tests with other raw materials, process operations and process conditions described in this specification, and all obtained relatively ideal results.

[0120] Although the present invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions and / or additions can be made without departing from the spirit and scope of the present invention and elements of the embodiments can be replaced with substantially equivalent ones. Additionally, many modifications can be made to adapt a particular situation or material to the teachings of the present invention without departing from the scope of the present invention. Therefore, it is not intended that the present invention be limited to the particular embodiments disclosed for carrying out the present invention, but rather that the present invention will include all embodiments falling within the scope of the appended claims. Further, unless specifically stated, any use of the terms first, second, etc. does not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. An addition amine curing agent that can be used for underwater curing, characterized in that: The structure of the addition amine curing agent is shown in Formula I: Wherein, R1 is selected from aliphatic groups, aromatic groups or polyether groups, n1 is an integer between 1 and 1000, n2 is an integer between 1 and 1000, m1 is an integer between 1 and 100, and m2 is an integer between 1 and 100.

2. A method for preparing an addition amine curing agent that can be used for underwater curing, characterized in that: include: A mixed reaction system containing chlorosulfonated polyethylene, diamine and an inactive diluent is subjected to an addition reaction to obtain a chlorosulfonated polyethylene addition amine curing agent.

3. The preparation method according to claim 2, characterized in that: The structure of the chlorosulfonated polyethylene is shown in Formula II: Wherein, n1 is an integer between 1 and 1000, n2 is an integer between 1 and 1000, m1 is an integer between 1 and 100, and m2 is an integer between 1 and 100; And / or, the number average molecular weight of the chlorosulfonated polyethylene is 10000-100000; And / or, the diamine includes one or a combination of aliphatic amine, aromatic amine, polyether amine, and alicyclic amine; And / or, the inactive diluent includes one or a combination of dibutyl phthalate, benzyl alcohol, phenylethyl alcohol, cashew nut shell oil polyol, and cardanol glycidyl ether; and / or, the reaction molar ratio of chlorosulfonated polyethylene to diamine in the mixed reaction system is 1:0.1-1; and / or, the reaction temperature is above 80°C, preferably 80-100°C; And / or, the reaction time is 3-5h.

4. An addition amine curing agent that can be used for underwater curing, characterized in that: It is prepared by the method described in claim 2 or 3.

5. Use of the addition amine curing agent for underwater curing according to claim 1 or 4 in the preparation of an underwater curable coating composition.

6. An underwater curable coating composition, characterized in that: It comprises a first component and a second component, wherein the mass ratio of the first component to the second component is 1:0.1-0.7; Wherein, the first component comprises 20-40wt% epoxy resin, 10-20wt% active diluent and 30-60wt% filler; The second component comprises 50-70 wt % of a curing agent and 30-50 wt % of an inactive diluent, wherein the curing agent comprises the addition amine curing agent of claim 1 or 4.

7. The coating composition according to claim 6, characterized in that: The epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and novolac epoxy resin; And / or, the active diluent includes one or a combination of two or more of allyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, octyl glycidyl ether, isopropyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, cardanol modified glycidyl ether, 1,4-butanediol glycidyl ether, propylene oxide butyl ether, and cardanol glycidyl ether; And / or, the filler includes one or a combination of two or more of rutile titanium dioxide, aluminum clay, talcum powder, silica powder, feldspar powder, mica powder, and barium sulfate; And / or, the first component further comprises 0.5-5wt% of an auxiliary agent, preferably, the auxiliary agent comprises a dispersant and / or a thixotropic agent.

8. Use of the coating composition according to claim 6 or 7 in preparing a protective coating, wherein the protective coating has at least an anti-corrosion function; Preferably, the protective coating is a protective coating used for equipment in a high humidity environment; More preferably, the protective coating is a protective coating for marine equipment; Preferably, the application includes: directly applying the coating composition to a substrate under water contact conditions to form a protective coating on the substrate or to maintain or repair the protective coating on the substrate.

9. A protective structure, formed on a substrate surface, for providing protection for the substrate, characterized in that: The protective structure comprises a protective coating formed from the coating composition according to any one of claims 6 or 7. Preferably, the substrate comprises a substrate for marine equipment; Preferably, the thickness of the protective coating is 300-5000 μm; Preferably, the substrate has a non-water-contacting area and / or a water-contacting area, the non-water-contacting area is an area of ​​the substrate that does not directly contact the water body under normal use conditions, and the water-contacting area is an area of ​​the substrate that directly contacts the water body under normal use conditions; when the protective structure is arranged in the non-water-contacting area of ​​the substrate, the thickness of the protective coating is 300-1500μm, more preferably 300-600μm; when the protective structure is arranged in the water-contacting area of ​​the substrate, the thickness of the protective coating is 500-4000μm, more preferably 1000-3000μm.

10. The coating method of the protective structure according to claim 9, characterized in that: include: The coating composition is applied to the surface of the substrate by at least one of manual coating or robot coating, wherein the coating method comprises one or more combinations of spraying, brushing, roller coating, scraping or smearing; Preferably, in the non-water contact area of ​​the substrate, the coating method is at least one of spraying, brushing or roller coating; in the water contact area of ​​the substrate, the coating method is at least one of roller coating, scraping or smearing; More preferably, an underwater robot is used to carry out scraping and / or smearing on the water contacting area of ​​the substrate.

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