Water-based epoxy primer for train and preparation method thereof

Abstract

The application relates to the technical field of epoxy primer, and discloses a water-based epoxy primer for trains and a preparation method thereof. The water-based epoxy primer for trains is prepared from diethanolamine, dodecafluoro-1,9-decadiene, maleic anhydride and the like as raw materials, and an intermediate 2 is prepared through reaction. The intermediate 2 is grafted into an epoxy resin under the initiation of an initiator. Phosphoric acid is introduced into the epoxy resin through ring-opening reaction with an epoxy group in the epoxy resin, and the water-based epoxy primer for trains is further prepared. The fluorine element is used to reduce the surface energy of the epoxy primer, so that the waterproof effect of the epoxy resin is improved. The phosphoric acid and the carboxyl structure are used to form a complex with a train metal base, so that the adhesion and the corrosion prevention effect of the epoxy resin are improved. The water-based epoxy primer prepared by the application has good waterproof effect and corrosion prevention effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy primer, in particular to a water-based epoxy primer for trains and a preparation method thereof. BACKGROUND

[0002] With the development of science and technology and the enhancement of world trade exchanges, the rail transportation industry, as a national pillar industry, is used in large quantities. Because the train will go through high cold, high heat, sand and other weather tests in the running process, a large amount of loss will be caused by corrosion, and energy waste is serious, so the corrosion resistance of the protective coating of the train vehicle is required to be high, and therefore how to improve the corrosion resistance of the protective primer for trains is one of the research hotspots.

[0003] The water-based epoxy coating is generally obtained by compounding epoxy resin, curing agent and the like, and has excellent adhesion and corrosion resistance, and is widely used in the fields of rail transportation, engineering equipment, marine corrosion prevention and the like, so in the use of train primer, the water-based epoxy primer is often used as protective coating.

[0004] A patent with application publication number CN 115975481 A discloses an epoxy resin anticorrosive coating and a preparation method thereof, which is prepared from epoxy resin, foamed graphene, polyamide curing agent and the like, and has good corrosion prevention effect, but does not improve the waterproof effect of the epoxy resin coating. SUMMARY

[0005] The present application aims to provide a water-based epoxy primer for trains and a preparation method thereof, which is modified by a water-based epoxy resin emulsion to enhance the waterproof and anticorrosive effects of the water-based epoxy primer, so as to solve the above-mentioned problems.

[0006] To achieve the above-mentioned purpose, the present application provides a water-based epoxy primer for trains, which comprises component A and component B, and the component A and the component B are separately packaged and mixed uniformly in a mass ratio of 4:1 when used.

[0007] Preferably, the component A is prepared from the following raw materials in parts by weight: fluorine-modified water-based epoxy resin emulsion 100 parts, dispersing agent 1-2.5 parts, defoaming agent 0.5-1 part, talc 5-15 parts, white carbon black 0.2-0.5 parts, wetting agent 0.4-1 part, rheological aid 0.2-0.5 parts, propylene glycol methyl ether 1-2 parts, deionized water 30-50 parts, thickening agent 1-2 parts, and anti-flash rust agent 0.5-1.5 parts.

[0008] Preferably, the preparation method of the component A comprises the following steps:

[0009] 1-2.5 parts by weight of a dispersant, 0.5-1 part by weight of an antifoaming agent, 5-15 parts by weight of talc, 0.2-0.5 parts by weight of white carbon black, 30-50 parts by weight of deionized water are added to a sand mill, and grinding is performed until the fineness is ≦30 μm, and then filtered, and 100 parts by weight of the fluorine-containing modified water-based epoxy resin emulsion, 0.4-1 part by weight of a wetting agent, 1-2 parts by weight of propylene glycol methyl ether, 0.2-0.5 parts by weight of a rheological aid, 1-2 parts by weight of a thickening agent, and 0.5-1.5 parts by weight of a flash rust preventive are added thereto, and stirring and dispersion are performed for 30 min to obtain the Part A component.

[0010] Preferably, the preparation method of the fluorine-containing modified water-based epoxy resin emulsion is:

[0011] (1) Diethanolamine is added to a toluene solvent, and stirring and dispersion are performed, and then dodecafluoro-1,9-decadiene is added thereto at 0-5°C, and stirring and mixing are performed until uniform, and then temperature is increased to perform reaction, and after the reaction is completed, distillation is performed under reduced pressure, and then washed with deionized water and dried to obtain intermediate 1, and the reaction synthesis route thereof is:

[0012]

[0013] (2) Maleic anhydride and intermediate 1 are added to a toluene solvent, and stirring and dispersion are performed, and then temperature is increased to 100-120°C, and stirring and reaction are performed for 2-5 h, and after the reaction is completed, distillation is performed under reduced pressure, and then washed with deionized water and dried to obtain intermediate 2, and the reaction synthesis route thereof is:

[0014]

[0015] (3) An epoxy resin is added to a n-butanol solvent, and stirring and dispersion are performed, and then temperature is increased to 75-85°C, and phosphoric acid is added thereto, and reaction is performed for 40-80 min, and then intermediate 2 and benzoyl peroxide are added thereto, and reaction is performed at 100-120°C for 5-8 h, and after the reaction is completed, temperature is decreased to 60-70°C, and N,N-dimethylethanolamine is added thereto to adjust the pH to 7-8, and finally deionized water is added thereto, and stirring and mixing are performed until uniform to obtain the fluorine-containing modified water-based epoxy resin emulsion.

[0016] Preferably, in the (1), the mass ratio of diethanolamine to dodecafluoro-1,9-decadiene is 60-80:100.

[0017] Preferably, in the (1), the temperature of the temperature-increasing reaction is 80-90°C, and the time is 20-50 min.

[0018] Preferably, in the (2), the mass ratio of maleic anhydride to intermediate 1 is 70-85:100.

[0019] Preferably, in the (3), the mass ratio of the epoxy resin, phosphoric acid, intermediate 2, benzoyl peroxide, deionized water is 100:3-5:10-30:5-10:150-200.

[0020] Preferably, the B component is a curing agent.

[0021] Reaction mechanism: the present application uses diethanolamine, dodecafluoro-1, 9-decadiene, maleic anhydride and the like as raw materials, and is prepared by reaction to obtain intermediate 2; the phosphoric acid attacks the epoxy ring in the epoxy resin, that is, the ring-opening reaction of phosphoric acid and epoxy occurs, the phosphoric acid is introduced into the epoxy resin, the benzoyl peroxide initiator initiates the graft polymerization of the active hydrogen on the secondary hydroxyl and methylene in the epoxy resin repeating segment and intermediate 2, and a fluorine-containing modified waterborne epoxy resin emulsion is obtained. Add the fluorine-containing modified waterborne epoxy resin emulsion, wetting agent, rheological aid and the like to the mixture of the ground dispersant, talc, white carbon black and the like, mix uniformly to obtain the A component, add the curing agent to it, and finally obtain the waterborne epoxy primer for trains.

[0022] The present application has the following advantages: the fluorine element used in the present application has a low surface energy, which can improve the waterproof and antifouling effect of the epoxy primer. The epoxy primer prepared by the present application contains phosphoric acid and carboxyl groups, which have a strong chelation effect with the metal base surface of the train, can complex with multivalent metal to form a complex, and can covalently bond the polymer to the metal base of the train to enhance the adhesion of the polymer coating on the metal base, and form a dense film on the metal surface of the train to achieve good corrosion resistance. The waterborne epoxy primer prepared by the present application has good waterproof effect and corrosion resistance. DETAILED DESCRIPTION

[0023] The following non-limiting examples can make those skilled in the art more fully understand the present application, but do not limit the present application in any way.

[0024] The epoxy resin is epoxy resin E-12;

[0025] The dispersant is dispersant BYK-190;

[0026] The defoaming agent is defoaming agent BYK-093;

[0027] The wetting agent is Tego4100 base wetting agent;

[0028] The rheological aid is 299 rheological aid;

[0029] The thickening agent is thickening agent GmbH Borchi 0620;

[0030] The anti-flash rust agent is anti-flash rust agent NALZIN FA179;

[0031] The curing agent is water-based epoxy curing agent HGH300.

[0032] Example 1

[0033] (1) According to parts by weight, 60 parts by weight of diethanolamine is added to toluene solvent, stirred and dispersed, 100 parts by weight of dodecafluoro-1, 9-decadiene is added at 0℃, stirred and mixed uniformly, warmed to 85℃, reacted for 30min, after the reaction is completed, distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1.

[0034] (2) According to parts by weight, 75 parts by weight of maleic anhydride, 100 parts by weight of intermediate 1 is added to toluene solvent, stirred and dispersed, warmed to 110℃, stirred and reacted for 4h, after the reaction is completed, distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 2.

[0035] (3) According to parts by weight, 100 parts by weight of epoxy resin is added to n-butanol solvent, stirred and dispersed, warmed to 75℃, 3 parts by weight of phosphoric acid is added, reacted for 60min, then 10 parts by weight of intermediate 2, 8 parts by weight of benzoyl peroxide is added, reacted for 8h at 110℃, after the reaction is completed, reduced to 70℃, N, N-dimethyl ethanolamine is added, adjusted to pH 7, finally 200 parts by weight of deionized water is added, stirred and mixed uniformly to obtain fluorine-containing modified water-based epoxy resin emulsion.

[0036] (4) According to parts by weight, 1.5 parts by weight of dispersant, 0.8 parts by weight of defoaming agent, 10 parts by weight of talc, 0.4 parts by weight of white carbon black, 40 parts by weight of deionized water is added to a sand mill, ground to a fineness of ≦30μm, filtered, then 100 parts by weight of fluorine-containing modified water-based epoxy resin emulsion, 0.5 parts by weight of wetting agent, 1.5 parts by weight of propylene glycol methyl ether, 0.4 parts by weight of rheological aid, 2 parts by weight of thickening agent, 1 part by weight of anti-flash rust agent is added, stirred and dispersed for 30min to obtain component A.

[0037] (5) When used, component A and component B are mixed uniformly in a ratio of 4:1 to obtain a water-based epoxy primer for trains.

[0038] Example 2

[0039] (1) According to parts by weight, 70 parts by weight of diethanolamine is added to toluene solvent, stirred and dispersed, 100 parts by weight of dodecafluoro-1, 9-decadiene is added at 0℃, stirred and mixed uniformly, warmed to 85℃, reacted for 40min, after the reaction is completed, distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1.

[0040] (2) According to weight parts, 80 parts by weight of maleic anhydride, 100 parts by weight of intermediate 1 are added to a toluene solvent, stirred and dispersed, heated to 120°C, stirred and reacted for 4h, after the reaction is completed, distilled under reduced pressure, washed with deionized water, dried, and intermediate 2 is obtained.

[0041] (3) According to weight parts, 100 parts by weight of epoxy resin are added to a n-butanol solvent, stirred and dispersed, heated to 85°C, 3.5 parts by weight of phosphoric acid is added thereto, and reacted for 80 min, then 15 parts by weight of intermediate 2, 5 parts by weight of benzoyl peroxide are added thereto, reacted at 120°C for 5h, after the reaction is completed, cooled to 60°C, N,N-dimethyl ethanolamine is added thereto, the pH is adjusted to 8, and finally 180 parts by weight of deionized water is added thereto, stirred and mixed uniformly to obtain a fluorine-containing modified water-based epoxy resin emulsion.

[0042] (4) According to weight parts, 1.5 parts by weight of dispersant, 0.8 parts by weight of defoaming agent, 12 parts by weight of talc, 0.4 parts by weight of white carbon black, 50 parts by weight of deionized water are added to a sand mill, ground, ground to a fineness of ≦30μm, filtered, then 100 parts by weight of fluorine-containing modified water-based epoxy resin emulsion, 0.4 parts by weight of wetting agent, 2 parts by weight of propylene glycol methyl ether, 0.4 parts by weight of rheological aid, 1 part by weight of thickening agent, 1.5 parts by weight of anti-flash rust agent are added thereto, stirred and dispersed for 30 min to obtain component A.

[0043] (5) When used, components A and B are mixed uniformly in a ratio of 4:1 to obtain a water-based epoxy primer for trains.

[0044] Example 3

[0045] (1) According to weight parts, 80 parts by weight of diethanolamine is added to a toluene solvent, stirred and dispersed, 100 parts by weight of dodecafluoro-1,9-decadiene is added thereto at 5°C, stirred and mixed uniformly, heated to 90°C, reacted for 20 min, after the reaction is completed, distilled under reduced pressure, washed with deionized water, dried, and intermediate 1 is obtained.

[0046] (2) According to weight parts, 75 parts by weight of maleic anhydride, 100 parts by weight of intermediate 1 are added to a toluene solvent, stirred and dispersed, heated to 110°C, stirred and reacted for 2h, after the reaction is completed, distilled under reduced pressure, washed with deionized water, dried, and intermediate 2 is obtained.

[0047] (3) According to weight parts, 100 parts by weight of epoxy resin is added to n-butanol solvent, stirred and dispersed, heated to 80°C, 4 parts by weight of phosphoric acid is added thereto, and reaction is kept for 40 min, then 20 parts by weight of intermediate 2 and 10 parts by weight of benzoyl peroxide are added thereto, and reaction is kept for 6 h at 100°C, after the reaction is completed, it is cooled to 65°C, N,N-dimethyl ethanolamine is added thereto to adjust pH to 7, and finally 150 parts by weight of deionized water is added thereto, and stirred and mixed uniformly to obtain fluorine-containing modified water-based epoxy resin emulsion.

[0048] (4) According to weight parts, 1 part by weight of dispersant, 1 part by weight of defoaming agent, 15 parts by weight of talc, 0.2 parts by weight of white carbon black, and 40 parts by weight of deionized water are added to a sand mill, and ground, and the ground product is filtered to a fineness of ≦30 μm, then 100 parts by weight of fluorine-containing modified water-based epoxy resin emulsion, 0.5 parts by weight of wetting agent, 2 parts by weight of propylene glycol methyl ether, 0.3 parts by weight of rheological aid, 2 parts by weight of thickening agent, and 0.5 parts by weight of anti-flash rust agent are added thereto, and stirred and dispersed for 30 min to obtain a component A.

[0049] (5) When used, the component A and component B are mixed uniformly at a ratio of 4:1 to obtain a water-based epoxy primer for trains.

[0050] Example 4

[0051] (1) According to weight parts, 70 parts by weight of diethanolamine is added to toluene solvent, stirred and dispersed, 100 parts by weight of dodecafluoro-1,9-decadiene is added thereto at 0°C, and stirred and mixed uniformly, and then heated to 80°C, and reaction is kept for 50 min, after the reaction is completed, it is distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1.

[0052] (2) According to weight parts, 85 parts by weight of maleic anhydride and 100 parts by weight of intermediate 1 are added to toluene solvent, stirred and dispersed, heated to 100°C, and stirred and reacted for 5 h, after the reaction is completed, it is distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 2.

[0053] (3) According to weight parts, 100 parts by weight of epoxy resin is added to n-butanol solvent, stirred and dispersed, heated to 80°C, 4.5 parts by weight of phosphoric acid is added thereto, and reaction is kept for 50 min, then 25 parts by weight of intermediate 2 and 8 parts by weight of benzoyl peroxide are added thereto, and reaction is kept for 6 h at 110°C, after the reaction is completed, it is cooled to 65°C, N,N-dimethyl ethanolamine is added thereto to adjust pH to 8, and finally 190 parts by weight of deionized water is added thereto, and stirred and mixed uniformly to obtain fluorine-containing modified water-based epoxy resin emulsion.

[0054] (4) According to parts by weight, 2.5 parts by weight of dispersant, 0.5 parts by weight of defoaming agent, 10 parts by weight of talc, 0.5 parts by weight of white carbon black, 30 parts by weight of deionized water are added to the sand mill, and grinding is carried out, and the grinding is carried out to a fineness ≦ 30 μm, and filtered, and then 100 parts by weight of fluorine-containing modified water-based epoxy resin emulsion, 1 part by weight of wetting agent, 2 parts by weight of propylene glycol methyl ether, 0.2 parts by weight of rheological aid, 1 part by weight of thickening agent, 1 part by weight of anti-flash rust agent are added, and stirred and dispersed for 30 min to obtain the A component.

[0055] (5) When in use, the A and B components are mixed uniformly in a ratio of 4:1 to obtain a water-based epoxy primer for trains.

[0056] Example 5

[0057] (1) According to parts by weight, 70 parts by weight of diethanolamine is added to toluene solvent, and stirred and dispersed, and then 100 parts by weight of dodecafluoro-1, 9-decadiene is added at 5 ℃, and stirred and mixed uniformly, and then warmed to 85 ℃, and reacted for 50 min, and after the reaction is completed, distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1.

[0058] (2) According to parts by weight, 70 parts by weight of maleic anhydride, 100 parts by weight of intermediate 1 are added to toluene solvent, and stirred and dispersed, and then warmed to 120 ℃, and stirred and reacted for 4 h, and after the reaction is completed, distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 2.

[0059] (3) According to parts by weight, 100 parts by weight of epoxy resin is added to n-butanol solvent, and stirred and dispersed, and then warmed to 80 ℃, and 5 parts by weight of phosphoric acid is added, and reacted for 50 min, and then 30 parts by weight of intermediate 2, 9 parts by weight of benzoyl peroxide are added, and reacted for 7 h at 110 ℃, and after the reaction is completed, lowered to 65 ℃, and N, N-dimethylethanolamine is added to adjust the pH to 8, and finally 200 parts by weight of deionized water is added, and stirred and mixed uniformly to obtain a fluorine-containing modified water-based epoxy resin emulsion.

[0060] (4) According to parts by weight, 2 parts by weight of dispersant, 0.6 parts by weight of defoaming agent, 5 parts by weight of talc, 0.4 parts by weight of white carbon black, 50 parts by weight of deionized water are added to the sand mill, and grinding is carried out, and the grinding is carried out to a fineness ≦ 30 μm, and filtered, and then 100 parts by weight of fluorine-containing modified water-based epoxy resin emulsion, 0.4 parts by weight of wetting agent, 1 part by weight of propylene glycol methyl ether, 0.5 parts by weight of rheological aid, 1.5 parts by weight of thickening agent, 1 part by weight of anti-flash rust agent are added, and stirred and dispersed for 30 min to obtain the A component.

[0061] (5) use, the two components are mixed evenly according to the proportion of 4:1, and the water-based epoxy primer for train is obtained.

[0062] Comparative Example 1

[0063] The difference between the present comparative example and Example 1 is that step (3) does not contain phosphoric acid.

[0064] Comparative Example 2

[0065] The difference between the present comparative example and Example 1 is that step (3) does not contain intermediate 2.

[0066] The water-based epoxy primer for train is evenly coated on a tinplate, placed at room temperature for 2h, then placed at 160℃ for 4h, taken out and placed at room temperature for 24h to obtain a paint film.

[0067] Adhesion performance test: according to GB / T9286-2021, the adhesion of the water-based epoxy primer is tested, 6 cutting lines are made on the test plate at intervals of 1mm, glass glue is pasted thereon, then removed, and the area of the paint film peeled off from the substrate is evaluated, which is divided into 0-5 levels, 0 being the best and 5 being the worst.

[0068] Corrosion performance test: the double-unit electrochemical workstation selected adopts a three-motor system, 3.5% NaCl solution is used as the test solution, platinum sheet is used as the auxiliary motor, saturated mercury is used as the reference motor, and the tinplate coated with the primer is used as the experimental electrode.

[0069] Waterproof performance test: the contact angle tester is used to measure the contact angle between the coating sample and water, and 5 points (distance not less than 1cm) are taken for each sample before measurement, and the average value is taken.

[0070] Table 1 Performance test

[0071]

[0072]

[0073] The greater the contact angle, the better the waterproof effect, the smaller the corrosion rate, and the better the corrosion protection effect. As can be seen from the table, the water-based epoxy primer prepared by the present application has good adhesion, corrosion protection effect and waterproof effect, the minimum corrosion rate can reach 0.00248mm / a, and the maximum contact angle can reach 108.6°.

[0074] For any skilled person familiar with the art, many possible variations and modifications of the technical solutions of the present application can be made using the technical content disclosed above without departing from the scope of the technical solutions of the present application, or modified as equivalent embodiments of equivalent changes. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application without departing from the content of the technical solutions of the present application shall still belong to the scope of protection of the technical solutions of the present application.

Claims

1. A water-based epoxy primer for trains, characterized in that: The water-based epoxy primer for trains comprises component A and component B, which are mixed evenly at a mass ratio of 4:1 when in use; The component A is prepared from the following raw materials in parts by weight: 100 parts of fluorine-modified waterborne epoxy resin emulsion, 1-2.5 parts of dispersant, 0.5-1 part of defoamer, 5-15 parts of talc, 0.2-0.5 parts of white carbon black, 0.4-1 parts of wetting agent, 0.2-0.5 parts of rheological additive, 1-2 parts of propylene glycol methyl ether, 30-50 parts of deionized water, 1-2 parts of thickener, and 0.5-1.5 parts of anti-flash rust agent; The preparation method of the component A comprises the following steps: 1-2.5 parts by weight of a dispersant, 0.5-1 parts by weight of a defoamer, 5-15 parts by weight of talc, 0.2-0.5 parts by weight of white carbon black, and 30-50 parts by weight of deionized water are added to a sand mill and ground to a fineness of ≦30 μm, filtered, and then 100 parts by weight of a fluorine-modified waterborne epoxy resin emulsion, 0.4-1 parts by weight of a wetting agent, 1-2 parts by weight of propylene glycol methyl ether, 0.2-0.5 parts by weight of a rheological additive, 1-2 parts by weight of a thickener, and 0.5-1.5 parts by weight of an anti-flash rust agent are added thereto, and the mixture is stirred and dispersed for 30 minutes to obtain component A; The component B is a curing agent; The preparation method of the fluorine-modified waterborne epoxy resin emulsion is: (1) Add diethanolamine to toluene solvent, stir and disperse, add dodecafluoro-1,9-decadiene at 0-5°C, stir and mix evenly, heat to react, and after the reaction is completed, distill under reduced pressure, wash with deionized water, and dry to obtain intermediate 1; (2) Add maleic anhydride and intermediate 1 to toluene solvent, stir and disperse, heat to 100-120°C, stir and react for 2-5 hours. After the reaction is completed, distill under reduced pressure, wash with deionized water, and dry to obtain intermediate 2; (3) Add the epoxy resin to n-butanol solvent, stir and disperse, heat to 75-85°C, add phosphoric acid, keep warm and react for 40-80 minutes, then add intermediate 2 and benzoyl peroxide, react at 100-120°C for 5-8 hours, after the reaction is completed, cool to 60-70°C, add N,N-dimethylethanolamine, adjust the pH to 7-8, finally add deionized water, stir and mix evenly to obtain a fluorine-modified waterborne epoxy resin emulsion.

2. The water-based epoxy primer for trains according to claim 1, characterized in that: In the above (1), the mass ratio of diethanolamine to dodecafluoro-1,9-decadiene is 60-80:

100.

3. The water-based epoxy primer for trains according to claim 1, characterized in that: In the above (1), the temperature of the temperature-raising reaction is 80-90°C and the time is 20-50 minutes.

4. The water-based epoxy primer for trains according to claim 1, characterized in that: In the above (2), the mass ratio of maleic anhydride to intermediate 1 is 70-85:

100.

5. The water-based epoxy primer for trains according to claim 1, characterized in that: In the above (3), the mass ratio of epoxy resin, phosphoric acid, intermediate 2, benzoyl peroxide and deionized water is 100:3-5:10-30:5-10:150-200.

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