A polyaspartic acid ester modified epoxy resin, a non-toxic, environmentally friendly, wear-resistant and anti-corrosion coating for ships containing the above resin, and its preparation method and application

Abstract

The present invention discloses a polyaspartic acid ester-modified epoxy resin, a non-toxic, environmentally friendly, wear-resistant, and anti-corrosion coating for ships containing the resin, as well as a preparation method and application. The structural formula of the polyaspartic acid ester-modified epoxy resin is as follows: The solvent-free, non-toxic, and anti-corrosion and anti-corrosion coating of the present invention uses the polyaspartic acid ester-modified epoxy resin as a film-forming material, can be cured at room temperature, and exhibits excellent adhesion, salt spray resistance, and media resistance. When applied to ship ballast tanks, drinking water tanks, oil and sewage tanks, and other compartments, or other metal substrate surfaces for corrosion protection, it provides excellent long-term anti-corrosion performance.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a polyaspartic acid ester modified epoxy resin, a marine non-toxic, environmentally friendly, wear-resistant and anti-corrosion coating containing the resin, and a preparation method and application thereof. Background Art

[0002] Epoxy resin is a high-molecular-weight polymer with excellent chemical resistance, especially alkali resistance. The resulting paint film has strong adhesion to inorganic materials such as cement and metal, and exhibits excellent mechanical properties, including resistance to wear, impact, organic solvents, heat, and water. The film is also non-toxic. However, it also suffers from drawbacks such as brittleness and poor weather resistance. Polyurethane modification is commonly performed by reacting the secondary hydroxyl groups of epoxy resin with isocyanates to incorporate polyols, etc., to improve the resin's initial adhesion, heat resistance, and hydrolytic stability. In this method, only the hydroxyl groups participate in the reaction, leaving the epoxy groups unaffected.

[0003] Spray polyurea elastomer (SPUA) technology is a novel, solvent-free, pollution-free, green construction technology developed and applied overseas over the past three decades to meet environmental protection needs, following low-pollution coatings (or non-pollution coatings) such as high-solids coatings, water-based coatings, radiation-cured coatings, and powder coatings. SPUA is based on reaction injection molding (RIM) technology and produces an elastomer with corrosion resistance, water resistance, and wear resistance, produced by the reaction of isocyanate and amino compounds. Polyaspartic acid ester polyurea, a third-generation polyurea elastomer, boasts low VOC, high solids content, long-lasting corrosion protection, and gloss and color retention. SPUA has been used in developed countries such as North America for over a decade and enjoys strong market demand.

[0004] At present, in the literature reports on solvent-free, non-toxic, long-lasting anti-corrosion and wear-resistant coatings for ships in my country, epoxy resin, polyurethane-modified epoxy resin, silicone-modified epoxy resin, etc. are basically used as the main film-forming materials. The performance of the prepared coatings hovers between long-term anti-corrosion and flexible and gloss-retaining properties, and the overall performance of the coating cannot be comprehensively improved.

[0005] Therefore, there is a need for a marine coating that is non-toxic, environmentally friendly, and can comprehensively improve the overall performance of the coating. Summary of the Invention

[0006] To address the problems of the prior art, the present invention provides a polyaspartic acid ester-modified epoxy resin, a non-toxic, environmentally friendly, wear-resistant, and anti-corrosion coating for marine applications containing the resin, as well as a preparation method and applications. The coating, which uses the polyaspartic acid ester-modified epoxy resin as a film-forming agent, cures at room temperature and exhibits excellent adhesion, salt spray resistance, and media resistance.

[0007] One of the objects of the present invention is to provide a polyaspartic acid ester modified epoxy resin.

[0008] The structural formula of the polyaspartic acid ester modified epoxy resin is as follows:

[0009]

[0010] Wherein, n is 1, 2, 3 or 4; R is -CH3 or X is —(CH2)6— or

[0011] A second object of the present invention is to provide a method for preparing the polyaspartic acid ester modified epoxy resin which is one of the objects of the present invention.

[0012] The method comprises:

[0013] The polyaspartic acid ester and the epoxy resin are stirred and reacted in the presence of a catalyst to obtain the polyaspartic acid ester modified epoxy resin.

[0014] In a preferred embodiment of the present invention,

[0015] The structure of the polyaspartic acid ester is:

[0016]

[0017] Wherein, R is -CH3 or X is —(CH2)6— or Preferably, at least one of F520, F420 of Shenzhen Feiyang Co., Ltd., JH-8152, and JH-8142 of Junhe Chemical (Shanghai) Co., Ltd.; and / or,

[0018] The structure of the epoxy resin is:

[0019]

[0020] Wherein, n is 1, 2, 3 or 4, preferably at least one of bisphenol A epoxy resins E51, E44 and E20; and / or,

[0021] The catalyst is n-butyl titanate.

[0022] In a preferred embodiment of the present invention,

[0023] The molar ratio of the polyaspartic acid ester to the epoxy resin is 1:1-15, preferably 1:4-14, and the sum of the weights of the two is 99-99.9wt% of the total feed amount, preferably 99-99.5wt%;

[0024] The weight of the catalyst is 0.1-1 wt% of the total feed amount, preferably 0.5-1 wt%.

[0025] In a preferred embodiment of the present invention,

[0026] The reaction temperature is 60-80°C, and the reaction time is 3-6 hours.

[0027] The third object of the present invention is to provide a marine non-toxic, environmentally friendly, wear-resistant and anti-corrosion coating containing the polyaspartic acid ester-modified epoxy resin of the first object of the present invention or the polyaspartic acid ester-modified epoxy resin prepared by the method of the second object of the present invention.

[0028] The coating is composed of a mixture of component A and component B;

[0029] The component A comprises: polyaspartic acid ester modified epoxy resin, pigments, fillers and additives;

[0030] Each component is calculated by weight.

[0031] 100 parts by weight of polyaspartic acid modified epoxy resin;

[0032] 60 to 140 parts by weight of pigments and fillers; preferably 70 to 140 parts by weight;

[0033] 1.8 to 4.5 parts by weight of auxiliary agent; preferably 2 to 4.2 parts by weight;

[0034] The B component includes: an amine curing agent and a curing accelerator;

[0035] Based on 100 parts by weight of polyaspartic acid ester modified epoxy resin,

[0036] 20 to 50 parts by weight of an amine curing agent; preferably 20 to 45 parts by weight;

[0037] 2 to 5 parts by weight of a curing accelerator;

[0038] The weight ratio of component A to component B is 1 to 10:1, preferably 3 to 8:1.

[0039] In a preferred embodiment of the present invention,

[0040] The pigments and fillers can be conventional pigments and fillers in the prior art and play a role of skeleton and corrosion protection. In the present invention, the pigments and fillers can preferably be at least one of rutile titanium dioxide with hiding ability, mica iron oxide, red iron oxide, aluminum powder, zinc phosphate, aluminum tripolyphosphate, functional filler nano-silica, precipitated barium sulfate, talc, mica powder, and calcium carbonate; and / or,

[0041] The auxiliary agent can be a conventional auxiliary agent in the prior art, which plays a role in improving the coating state. In the present invention, it can preferably be at least one of a defoamer, a leveling agent, a wetting and dispersing agent, and a coupling agent. The defoamer is preferably one or more of BYK-066N, BYK-A530, AFCONA2720, AFCONA2723, and AFCONA2020. The leveling agent is preferably one or more of BYK-320, AFCONA3700, and AFCONA3770. The wetting and dispersing agent is preferably one or more of BYK-P104S, BYK-354, and BYK-378. The coupling agent is preferably one or more of KH-550, KH-560, and KH-570. And / or,

[0042] The amine curing agent is at least one of modified amine curing agents of aromatic amine and aliphatic amine, preferably at least one of modified amine curing agents of diethylenetriamine, m-phenylenediamine, isophoronediamine and diaminodiphenylmethane, more preferably at least one of R-2258 and R-2259 of Guangzhou Ruiqi Company, JH5952 and JH5390G of Jiadida Company, and Ancamine2280 of Air Chemical Company; and / or,

[0043] The curing accelerator can be a conventional curing accelerator in the prior art. In the present invention, DMP-30 curing accelerator is preferably used.

[0044] The fourth object of the present invention is to provide a method for preparing the coating of the third object of the present invention.

[0045] The method comprises:

[0046] First, the components A and B are mixed according to the amounts of the components respectively, and then the components A and B are mixed according to the amount ratio to prepare the non-toxic, environmentally friendly, wear-resistant and anti-corrosion coating for ships.

[0047] The fifth object of the present invention is to provide a coating according to the third object of the present invention or a coating prepared by the method according to the fourth object of the present invention for use in the anti-corrosion protection of ship ballast tanks, drinking water tanks, oil and sewage tanks and other cabins or other metal substrate surfaces.

[0048] The present invention can specifically adopt the following technical solutions:

[0049] The polyaspartic acid ester modified epoxy resin of the present invention is synthesized by grafting polyaspartic acid ester with epoxy resin, and can be preferably prepared according to the following method:

[0050] The catalyst is slowly added dropwise to the polyaspartic acid ester and epoxy resin under stirring at 60-80°C. After the addition is completed, the mixture is reacted for 3-6 hours and cooled to 40°C to obtain a low-viscosity solution, which is the polyaspartic acid ester modified epoxy resin.

[0051] The non-toxic, environmentally friendly, wear-resistant and anti-corrosion coating for ships can be preferably prepared according to the following method:

[0052] Prepare component A first: Mix the polyaspartic acid ester modified epoxy resin, pigments, fillers and additives according to the above ratio, then grind them into 40-80 μm using a sand mill or a three-roll mill, filter them with a filter, and pack them in a measured amount.

[0053] Then prepare component B: mix the amine curing agent and the curing accelerator according to the above ratio;

[0054] The A and B components are uniformly mixed in a weight ratio of 1-10:1 to obtain the marine non-toxic, environmentally friendly, wear-resistant and anti-corrosion coating.

[0055] The principles of the present invention are as follows:

[0056] The invention controls specific temperature and time to open the epoxy ring of the amino group of polyaspartic acid ester, thereby preparing the polyaspartic acid ester modified epoxy resin.

[0057] The beneficial effects of the present invention are as follows:

[0058] The coating composition of the present invention may be applied by brushing, rolling or spraying.

[0059] The solvent-free, non-toxic, anti-corrosion and wear-resistant coating of the present invention can be cured at room temperature and applied to ship ballast tanks, drinking water tanks, oil and sewage tanks, and other compartments, or other metal substrate surfaces for corrosion protection, providing excellent long-term corrosion protection.

[0060] The total coating thickness of the dry film of the present invention is controlled at 200 μm, which can achieve satisfactory results.

[0061] The solvent-free, non-toxic, anti-corrosion and wear-resistant coating prepared by the present invention has the following excellent comprehensive properties:

[0062] Flexibility (level): 1;

[0063] Adhesion (level): 1;

[0064] Salt spray resistance: 3000 hours of coating without blistering, peeling or discoloration;

[0065] Medium resistance: (seawater, saturated salt water, tap water, lubricating oil, engine oil, diesel) The coating will not bubble, fall off or rust for 3 months. DETAILED DESCRIPTION

[0066] The present invention will be described in detail below with reference to specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0067] The raw materials used in the examples are all conventional commercially available raw materials.

[0068] The performance testing method in the embodiment of the present invention is as follows:

[0069] Flexibility (grade): GB / T1731-2020 Determination of flexibility of paint film and putty film;

[0070] Adhesion (grade): GB / T9286-1998 cross-cut test for paint and varnish films;

[0071] Salt spray resistance: GB / T1771-2007 Determination of neutral salt spray resistance of paints and varnishes;

[0072] Medium resistance: GB / T9274-1988 Determination of resistance of paints and varnishes to liquid media.

[0073] The infrared absorption spectrum in the embodiments of the present invention was measured by a Shimadzu IRPrestige-21 infrared spectrometer.

[0074] Example 1

[0075] 20 parts by weight of F520 polyaspartic acid ester and 79 parts by weight of E44 epoxy resin (molar ratio of 1:5) from Shenzhen Feiyang Company were stirred evenly, slowly heated to 80°C, and then 1 part by weight of n-butyl titanate was added dropwise to the reactor. After the addition was completed, the mixture was reacted for 6 hours, cooled to 40°C, and discharged to obtain a low-viscosity solution, which is the polyaspartic acid ester modified epoxy resin. The viscosity of the solution was determined by infrared absorption spectroscopy at 1728cm -1 、1660cm -1 and 1542cm -1 The characteristic absorption peak of aspartic acid ester urethane bond appears, and 918cm -1 and 910cm -1 The characteristic absorption peak of the epoxy group nearby weakened, which indicated that the epoxy group was consumed, and the appearance of the urethane bond indicated that the amino group opened the epoxy ring and grafted successfully, thus proving that the polyaspartic acid ester-modified epoxy resin was obtained through the synthesis reaction.

[0076] Example 2

[0077] 10 parts by weight of JH-8142 polyaspartic acid ester from Junhe Chemical Company and 89.5 parts by weight of E51 epoxy resin (molar ratio of 1:13) were stirred evenly, slowly heated to 60°C, and then 0.5 parts by weight of n-butyl titanate was added dropwise to the reactor. After the addition was completed, the mixture was reacted for 3 hours, cooled to 40°C, and discharged to obtain a low-viscosity solution, which is the polyaspartic acid ester modified epoxy resin. The viscosity of the solution was determined by infrared absorption spectroscopy at 1728 cm -1 、1660cm -1 and 1542cm -1 The characteristic absorption peak of aspartic acid ester urethane bond appears, and 918cm -1 and 910cm -1 The characteristic absorption peak of the epoxy group nearby is weakened, proving that polyaspartic acid ester modified epoxy resin is obtained through the synthesis reaction.

[0078] Example 3

[0079] 19 parts by weight of F420 polyaspartic acid ester and 80.5 parts by weight of E20 epoxy resin (molar ratio of 1:6) from Shenzhen Feiyang Company were stirred evenly, slowly heated to 60°C, and then 0.5 parts by weight of n-butyl titanate was added dropwise to the reactor. After the addition was completed, the reaction was continued for 3 hours, and the mixture was cooled to 40°C and discharged to obtain a low-viscosity solution, which is the polyaspartic acid ester modified epoxy resin. The viscosity of the solution was determined by infrared absorption spectroscopy at 1728cm -1 、1660cm -1 and 1542cm -1 The characteristic absorption peak of aspartic acid ester urethane bond appears, and 918cm -1 and 910cm -1 The characteristic absorption peak of the epoxy group nearby is weakened, proving that polyaspartic acid ester modified epoxy resin is obtained through the synthesis reaction.

[0080] Example 4

[0081] 100 parts by weight of the polyaspartic acid ester-modified epoxy resin of Example 1 was weighed and put into a stainless steel tank with a high-speed stirrer for stirring. 0.6 parts by weight of a defoamer (BYK066N), 0.8 parts by weight of a wetting and dispersing agent (BYKP104S), 0.4 parts by weight of a leveling agent (BYK320), and 0.2 parts by weight of a coupling agent (KH550) were added and stirred evenly with the resin. Then, 30 parts by weight of mica iron oxide, 5 parts by weight of red iron oxide, 15 parts by weight of aluminum tripolyphosphate, 5 parts by weight of precipitated barium sulfate, and 15 parts by weight of mica powder were added and stirred evenly. The mixture was then ground to a standard fineness using a sand mill or a three-roll mill, and filtered and packaged as component A of the coating.

[0082] Weigh 40 parts by weight of R-2258 (Guangzhou Ruiqi Company) and 3 parts by weight of DMP-30 curing accelerator and stir them evenly to obtain component B of the coating.

[0083] When in use, mix components A and B in a weight ratio of 4:1 and spray them. After curing at room temperature for seven days, a solvent-free, non-toxic, environmentally friendly, anti-corrosion and wear-resistant coating with a coating thickness of 200μm is obtained.

[0084] The test results of the performance of the solvent-free, non-toxic, environmentally friendly, anti-corrosion and wear-resistant coating prepared in Example 4 are as follows:

[0085] Flexibility (level): 1

[0086] Adhesion (level): 1;

[0087] Salt spray resistance: 3000 hours of coating without blistering, peeling or discoloration;

[0088] Medium resistance: (seawater, saturated salt water, tap water, lubricating oil, engine oil, diesel) The coating will not bubble, fall off or rust for 3 months.

[0089] Example 5

[0090] 100 parts by weight of the polyaspartic acid ester-modified epoxy resin of Example 1 was weighed and put into a stainless steel tank with a high-speed stirrer for stirring. 1.2 parts by weight of a defoamer (BYKA530), 1.2 parts by weight of a wetting and dispersing agent (BYK354), 0.8 parts by weight of a leveling agent (AFCONA3700), and 1 part by weight of a coupling agent (KH560) were added and stirred evenly with the resin. Then, 30 parts by weight of aluminum powder, 30 parts by weight of red iron oxide, 15 parts by weight of zinc phosphate, 10 parts by weight of nano-silicon dioxide, and 15 parts by weight of calcium carbonate were added and stirred evenly. The mixture was then ground to a standard fineness using a sand mill or a three-roll grinder, and filtered and packaged as component A of the coating.

[0091] Weigh 20 parts by weight of Ancamine 2280 (Air Chemicals) and 5 parts by weight of DMP-30 curing accelerator and stir them evenly to obtain component B of the coating.

[0092] When in use, mix components A and B in a weight ratio of 8:1 and spray them. After curing at room temperature for seven days, a solvent-free, non-toxic, environmentally friendly, anti-corrosion and wear-resistant coating with a coating thickness of 200μm is obtained.

[0093] The test results of the performance of the solvent-free, non-toxic, environmentally friendly, anti-corrosion and wear-resistant coating prepared in Example 5 are as follows:

[0094] Flexibility (level): 1

[0095] Adhesion (level): 1;

[0096] Salt spray resistance: 3000 hours of coating without blistering, peeling or discoloration;

[0097] Medium resistance: (seawater, saturated salt water, tap water, lubricating oil, engine oil, diesel) The coating will not bubble, fall off or rust for 3 months.

[0098] Example 6

[0099] 100 parts by weight of the polyaspartic acid ester modified epoxy resin of Example 2 was weighed and put into a stainless steel tank with a high-speed stirrer for stirring. 0.8 parts by weight of a defoamer (AFCONA2720), 0.6 parts by weight of (AFCONA2020), 0.8 parts by weight of a wetting and dispersing agent (BYK378), 0.8 parts by weight of a leveling agent (AFCONA3770), and 0.5 parts by weight of a coupling agent (KH570) were added. After stirring evenly with the resin, 50 parts by weight of mica iron oxide, 30 parts by weight of red iron oxide, 20 parts by weight of zinc phosphate, 20 parts by weight of nano-silica, and 20 parts by weight of mica powder were added and stirred evenly. The mixture was then ground to a standard fineness with a sand mill or a three-roll grinder, and filtered and packaged as component A of the coating.

[0100] Weigh 45 parts by weight of JH5952 (from Jiadida Company) and 3.7 parts by weight of DMP-30 curing accelerator and stir them evenly to obtain component B of the coating.

[0101] When in use, mix components A and B in a weight ratio of 5:1 and spray them. After curing at room temperature for seven days, a solvent-free, non-toxic, environmentally friendly, anti-corrosion and wear-resistant coating with a coating thickness of 200μm is obtained.

[0102] The test results of the performance of the solvent-free, non-toxic, environmentally friendly, anti-corrosion and wear-resistant coating prepared in Example 6 are as follows:

[0103] Flexibility (level): 1

[0104] Adhesion (level): 1;

[0105] Salt spray resistance: 3000 hours of coating without blistering, peeling or discoloration;

[0106] Medium resistance: (seawater, saturated salt water, tap water, lubricating oil, engine oil, diesel) The coating will not bubble, fall off or rust for 3 months.

[0107] Example 7

[0108] Weigh 100 parts by weight of the polyaspartic acid ester modified epoxy resin of Example 2, put it into a stainless steel tank and stir it with a high-speed stirrer, add 0.6 parts by weight of a defoamer (AFCONA2723), 0.6 parts by weight of (AFCONA2020), 0.8 parts by weight of a wetting and dispersing agent (BYKP104S), 0.6 parts by weight of a leveling agent (AFCONA3700), and 0.4 parts by weight of a coupling agent (KH560), stir evenly with the resin, then add 30 parts by weight of iron oxide red, 15 parts by weight of aluminum tripolyphosphate, 15 parts by weight of zinc phosphate, 5 parts by weight of nano-silica, and 15 parts by weight of mica powder and stir evenly, then grind to a standard fineness with a sand mill or a three-roll grinder, and filter and package as component A of the coating.

[0109] Weigh 28.5 parts by weight of JH5390G (Jiadida Company) and 2 parts by weight of DMP-30 curing accelerator and stir them evenly to obtain component B of the coating.

[0110] When in use, mix components A and B in a weight ratio of 6:1 and spray them. After curing at room temperature for seven days, a solvent-free, non-toxic, environmentally friendly, anti-corrosion and wear-resistant coating with a coating thickness of 200μm is obtained.

[0111] The test results of the solvent-free, non-toxic, anti-corrosion, environmentally friendly, and wear-resistant coating prepared in Example 7 are as follows:

[0112] Flexibility (level): 1

[0113] Adhesion (level): 1;

[0114] Salt spray resistance: 3000 hours of coating without blistering, peeling or discoloration;

[0115] Medium resistance: (seawater, saturated salt water, tap water, lubricating oil, engine oil, diesel) The coating will not bubble, fall off or rust for 3 months.

[0116] Comparative Example 1

[0117] Weigh 100 parts by weight of E44 epoxy resin, put it into a stainless steel tank with a high-speed stirrer, add 0.6 parts by weight of the same defoamer (AFCONA2723), 0.6 parts by weight of (AFCONA2020), 0.8 parts by weight of wetting and dispersing agent (BYKP104S), 0.6 parts by weight of leveling agent (AFCONA3700), and 0.4 parts by weight of coupling agent (KH560) as in Example 6, stir evenly with the resin, then add 30 parts by weight of iron oxide red, 15 parts by weight of aluminum tripolyphosphate, 15 parts by weight of zinc phosphate, 5 parts by weight of nano-silica, and 15 parts by weight of mica powder, stir evenly, then grind to standard fineness with a sand mill or a three-roll grinder, filter and package as coating component A.

[0118] Weigh 60 parts by weight of JH5390G (Jiadida Company) and 1 part by weight of DMP-30 curing accelerator and stir them evenly to obtain component B of the coating.

[0119] When in use, components A and B are evenly mixed in a weight ratio of 3:1 and then sprayed. After curing at room temperature for seven days, a coating with a coating thickness of 200 μm is obtained.

[0120] The test results of the coating performance prepared in Comparative Example 1 are as follows:

[0121] Flexibility (level): 3;

[0122] Adhesion (level): 2;

[0123] Salt spray resistance: 3000 hours of coating without blistering, peeling or discoloration;

[0124] Medium resistance: (seawater, saturated salt water, tap water, lubricating oil, engine oil, diesel) The coating will not bubble, fall off or rust for 3 months.

[0125] Comparative Example 2

[0126] Weigh 100 parts by weight of a commercially available silicone-modified epoxy resin (Zhonghao Chenguang HG-43), put it into a stainless steel tank and stir it with a high-speed stirrer, add 0.6 parts by weight of the same defoamer (AFCONA2723) and (AFCONA2020), 0.8 parts by weight of a wetting and dispersing agent (BYKP104S), 0.6 parts by weight of a leveling agent (AFCONA3700), and 0.4 parts by weight of a coupling agent (KH560) as in Example 6, stir evenly with the resin, then add 30 parts by weight of iron oxide red, 15 parts by weight of aluminum tripolyphosphate, 15 parts by weight of zinc phosphate, 5 parts by weight of nano-silica, and 15 parts by weight of mica powder and stir evenly, then grind to a standard fineness with a sand mill or a three-roll grinder, filter and package as component A of the coating.

[0127] Weigh 28.5 parts by weight of JH5390G (Jiadida Company) and 1 part by weight of DMP-30 curing accelerator and stir them evenly to obtain component B of the coating.

[0128] When in use, components A and B are evenly mixed in a weight ratio of 6:1 and then sprayed. After curing at room temperature for seven days, a coating with a coating thickness of 200 μm is obtained.

[0129] The test results of the coating performance prepared in Comparative Example 2 are as follows:

[0130] Flexibility (level): 1

[0131] Adhesion (level): 2;

[0132] Salt spray resistance: coating blistering after 2000 hours;

[0133] Medium resistance: (seawater, saturated salt water, tap water, lubricating oil, engine oil, diesel) The coating will bubble and rust after 1 month.

[0134] It can be seen from Examples 1-7 that the solvent-free, non-toxic, anti-corrosion and wear-resistant coating of the present invention can be cured at room temperature, has excellent adhesion, salt spray resistance and medium resistance, and is used for anti-corrosion protection of ship ballast tanks, drinking water tanks, oil and sewage tanks and other compartments, or other metal substrate surfaces, and can provide excellent long-term anti-corrosion performance.

[0135] It can be seen from Comparative Examples 1-2 that the flexibility and adhesion of the coating prepared using unmodified epoxy resin need to be improved; the flexibility of the coating prepared using silicone-modified epoxy resin is improved compared to epoxy resin, but the salt spray resistance and medium resistance are reduced; and the solvent-free, non-toxic, anti-corrosion and wear-resistant coating prepared using the polyaspartic acid ester modified epoxy resin of the present invention has good flexibility, adhesion, salt spray resistance and medium resistance, and can provide long-term anti-corrosion performance.

Claims

1. A polyaspartic acid ester modified epoxy resin, characterized in that: The structural formula of the polyaspartic acid ester modified epoxy resin is as follows: Wherein, n is 1, 2, 3 or 4; R is -CH3 or X is —(CH2)6— or The preparation method of the polyaspartic acid ester modified epoxy resin comprises: stirring and reacting polyaspartic acid ester and epoxy resin in the presence of a catalyst to obtain the polyaspartic acid ester modified epoxy resin; the catalyst is n-butyl titanate, the molar ratio of the polyaspartic acid ester to the epoxy resin is 1:4-14, and the reaction temperature is 60-80°C.

2. A method for preparing a polyaspartic acid ester modified epoxy resin as claimed in claim 1, characterized in that The method comprises: Stirring polyaspartic acid ester and epoxy resin to react in the presence of a catalyst to obtain the polyaspartic acid ester modified epoxy resin; The structure of the polyaspartic acid ester is: Wherein, R is -CH3 or X is —(CH2)6— or and / or, The structure of the epoxy resin is: wherein n is 1, 2, 3 or 4; and / or, The catalyst is n-butyl titanate; the molar ratio of the polyaspartic acid ester to the epoxy resin is 1:4-14; and the reaction temperature is 60-80°C.

3. The preparation method according to claim 2, wherein: The sum of the weight of the polyaspartic acid ester and the epoxy resin is 99-99.9 wt% of the total input amount; The weight of the catalyst is 0.1-1 wt% of the total feed amount.

4. The preparation method according to claim 2, wherein: The reaction time is 3 to 6 hours.

5. A non-toxic, environmentally friendly, wear-resistant and anti-corrosion coating for ships containing the polyaspartic acid ester-modified epoxy resin according to claim 1 or the polyaspartic acid ester-modified epoxy resin prepared by the method according to any one of claims 2 to 4, characterized in that: The coating is composed of a mixture of component A and component B; The component A comprises: polyaspartic acid ester modified epoxy resin, pigments, fillers and additives; Each component is calculated by weight. 100 parts by weight of polyaspartic acid modified epoxy resin; 60-140 parts by weight of pigments and fillers; 1.8 to 4.5 parts by weight of auxiliary agent; The B component includes: an amine curing agent and a curing accelerator; Based on 100 parts by weight of polyaspartic acid ester modified epoxy resin, 20-50 parts by weight of an amine curing agent; 2 to 5 parts by weight of a curing accelerator; The weight ratio of component A to component B is 1 to 10:

1.

6. The coating according to claim 5, wherein: 100 parts by weight of polyaspartic acid modified epoxy resin; 70-140 parts by weight of pigments and fillers; 2 to 4.2 parts by weight of auxiliary agent; Based on 100 parts by weight of polyaspartic acid ester modified epoxy resin, 20-45 parts by weight of an amine curing agent; 2 to 5 parts by weight of a curing accelerator; The weight ratio of component A to component B is 3 to 8:

1.

7. The coating according to claim 5, wherein: The auxiliary agent is at least one of a defoaming agent, a leveling agent, a wetting and dispersing agent, and a coupling agent; and / or, The amine curing agent is at least one of modified amine curing agents of aromatic amine and aliphatic amine.

8. The coating according to claim 7, wherein: The amine curing agent is at least one of modified amine curing agents selected from diethylenetriamine, m-xylenediamine, isophoronediamine and diaminodiphenylmethane.

9. A method for preparing a coating according to any one of claims 5 to 8, characterized in that The method comprises: First, the components A and B are mixed according to the amounts of the components respectively, and then the components A and B are mixed according to the amount ratio to prepare the non-toxic, environmentally friendly, wear-resistant and anti-corrosion coating for ships.

10. Use of the coating according to any one of claims 5 to 8 or the coating prepared by the method according to claim 9 for anti-corrosion protection of ship ballast tanks, drinking water tanks, oil and sewage tanks or other metal substrate surfaces.

Images