Degreasing and antirust two-in-one washing-free zero-emission pretreatment agent and application thereof in enamel

Abstract

The invention belongs to the technical field of emission-free enamel pretreatment, and particularly relates to a degreasing and antirust two-in-one washing-free zero-emission pretreatment agent and application thereof in enamel. The degreasing and antirust two-in-one washing-free zero-emission pretreatment agent is prepared from the following components in parts by weight: 5 to 10 parts of anionic water dispersible epoxy ester resin, 1 to 1.5 parts of an acid-base regulator, 3 to 5 parts of a degreasing agent and 83.5 to 91 parts of pure water, the pH value is 8-11, and the solid content is 0.03-0.3%. The degreasing and rust prevention two-in-one washing-free zero-emission pretreatment agent is prepared, only one tank is needed in the whole technological process when the pretreatment agent is applied to enamel pretreatment, the surface degreasing and rust prevention effects can be achieved without washing after pretreatment is completed, meanwhile, the residual pretreatment agent does not affect the appearance effect of enamel, and the pretreatment agent is environmentally friendly. And various test effects of the enamel are not influenced. Compared with a traditional enamel pretreatment process, the pretreatment quality is improved, water and electricity resources are saved, emission is reduced, and potential health hazards caused to users are reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of emission-free enamel pretreatment, and in particular relates to a two-in-one degreasing and rust-proofing water-free and zero-emission pretreatment agent and application thereof in enamel. Background Art

[0002] Enamel pretreatment refers to a series of treatment steps performed on the metal surface before enamel coating to ensure that the enamel glaze can be firmly attached to the metal surface. The main enamel pretreatment methods include sandblasting, air firing (thermal degreasing method) and chemical cleaning.

[0003] The traditional chemical cleaning method for enamel pretreatment mainly includes two steps: degreasing and pickling. The pretreatment agent is used to perform the pretreatment using a chemical degreasing-water washing-sodium nitrite process. The traditional enamel pretreatment has the following problems: (1) A large amount of wastewater is generated during the pretreatment process, which pollutes the environment; (2) The pretreatment agent needs to undergo complex treatment after use to meet environmental emission standards; (3) Long-term contact with pretreatment agents such as sodium nitrite will also pose health risks to users. Therefore, the existence of the above problems has led to the traditional enamel pretreatment increasing the processing cost and operating difficulty of enterprises.

[0004] Therefore, from the perspective of environmental protection and sustainable development of enamel pretreatment technology, it is necessary to develop a two-in-one degreasing and rust-proofing water-free and zero-emission pretreatment agent. Summary of the invention

[0005] In order to solve the above-mentioned problems in the prior art, the present invention provides a two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention and its application in enamel, and prepares a two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention. Compared with the traditional enamel pretreatment process, the quality of pretreatment is improved, water and electricity resources are saved, emissions are reduced, and health risks to users are reduced.

[0006] In order to achieve the above object, the main technical solutions adopted by the present invention include:

[0007] According to the first aspect of the present invention: a two-in-one degreasing and rust-proofing water-free zero-emission pretreatment agent, in parts by weight: comprising 5-10 parts by weight of anionic water-dispersible epoxy ester resin, 1-1.5 parts by weight of acid-base regulator, 3-5 parts by weight of degreasing agent and 83.5-91 parts by weight of pure water;

[0008] The pH value of the two-in-one water-free, zero-emission pre-treatment agent for degreasing and rust prevention is 8-11, and the solid content is 0.03-0.3%.

[0009] Furthermore, the preparation method of the two-in-one water-free and zero-emission pretreatment agent for degreasing and rust prevention is as follows:

[0010] Add anionic water-dispersible epoxy ester resin and degreasing agent into a clean reactor and stir, then add acid-base regulator and stir evenly, finally add pure water and stir for 30-60 minutes to obtain a two-in-one degreasing and rust-proofing water-free zero-emission pretreatment agent.

[0011] Further, the acid-base regulator is one or more of dimethylethanolamine, ethanolamine and triethanolamine;

[0012] The degreasing agent is one or more of ethylene glycol monobutyl ether, propylene glycol methyl ether and n-butanol.

[0013] Furthermore, the anionic water-dispersible epoxy ester resin comprises 40-45 parts by weight of oleic acid-modified epoxy resin, 10-12 parts by weight of solvent, 0.3-0.5 parts by weight of initiator, 3.6-4 parts by weight of acrylic monomer mixture and 1.6-1.8 parts by weight of neutralizer; the acid value of the anionic water-dispersible epoxy ester resin is less than 15.

[0014] Further, the preparation method of anionic water-dispersible epoxy ester resin is as follows:

[0015] Put oleic acid modified epoxy resin and solvent into a clean reactor and stir, heat to 120-130°C, add acrylic monomer mixture and initiator, react at 120-130°C for 3-4h to obtain acrylic modified epoxy resin, then cool to 60-80°C, add neutralizer and stir to react for 45-75min to obtain anionic water-dispersible epoxy ester resin.

[0016] Further, the acrylic monomer mixture includes acrylic acid, styrene and methyl acrylate, and the weight ratio of acrylic acid, styrene and methyl acrylate is 1:2:0.6;

[0017] The initiator is 2,2-di(tert-butylperoxy)butane;

[0018] The solvent is n-butanol;

[0019] The neutralizing agent is dimethylethanolamine.

[0020] Further, the oleic acid-modified epoxy resin comprises 13-15 parts by weight of bisphenol A epoxy resin, 0.02-0.05 parts by weight of a catalyst and 30-35 parts by weight of oleic acid;

[0021] The acid value of the oleic acid-modified epoxy resin is less than 20.

[0022] Further, the preparation method of oleic acid modified epoxy resin is as follows:

[0023] Add bisphenol A epoxy resin and catalyst into a clean reactor and stir, heat to 140-150°C, add oleic acid, and carry out esterification reaction at 140-150°C for 3-4 hours to obtain oleic acid-modified epoxy resin.

[0024] Further, the bisphenol A epoxy resin is E12;

[0025] The catalyst is zinc oxide;

[0026] The oleic acid is dehydrated ricinoleic acid and linoleic acid, and the weight ratio of the dehydrated ricinoleic acid to the linoleic acid is 7:3.

[0027] According to the second aspect of the present invention, a two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention is used in enamel. The above-mentioned two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention is put into an enamel pretreatment tank to perform degreasing and rust prevention treatment on the workpiece. The enamel pretreatment tank is a two-in-one degreasing and rust prevention tank and the number is 1-3.

[0028] The beneficial effects of the present invention are:

[0029] (1) A two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention was prepared. When applied to enamel pretreatment, the overall process only requires one to three tanks. After the pretreatment is completed, no water washing is required to achieve the effect of surface degreasing and rust prevention. At the same time, the residual pretreatment agent does not affect the appearance of the enamel, nor does it affect the various test results of the enamel.

[0030] (2) Compared with traditional enamel pretreatment technology, it saves water and electricity resources, reduces emissions, and reduces health risks to users. DETAILED DESCRIPTION

[0031] In order to better explain the present invention and facilitate understanding, the present invention is described in detail below through specific implementation methods.

[0032] In order to illustrate the scheme and technical advancement of the present invention, the technical scheme and technical application designed are as follows:

[0033] According to the first aspect of the present invention, a two-in-one degreasing and rust-proofing water-free and zero-emission pre-treatment agent comprises, in parts by weight: 5-10 parts by weight of anionic water-dispersible epoxy ester resin, 1-1.5 parts by weight of acid-base regulator, 3-5 parts by weight of degreasing agent and 83.5-91 parts by weight of pure water; wherein: the acid-base regulator is one or more of dimethylethanolamine, ethanolamine and triethanolamine; the degreasing agent is one or more of ethylene glycol monobutyl ether, propylene glycol methyl ether and n-butanol; the pH value of the two-in-one degreasing and rust-proofing water-free and zero-emission pre-treatment agent is 8-11, and the solid content is 0.03-0.3%.

[0034] The preparation method of the two-in-one water-free and zero-emission pretreatment agent for degreasing and rust prevention is as follows:

[0035] Add anionic water-dispersible epoxy ester resin and degreasing agent into a clean reactor and stir, then add acid-base regulator and stir evenly, finally add pure water and stir for 30-60 minutes to obtain a two-in-one degreasing and rust-proofing water-free zero-emission pretreatment agent.

[0036] Preferably, the anionic water-dispersible epoxy ester resin comprises 40-45 parts by weight of oleic acid-modified epoxy resin, 10-12 parts by weight of solvent, 0.3-0.5 parts by weight of initiator, 3.6-4 parts by weight of acrylic monomer mixture and 1.6-1.8 parts by weight of neutralizer; wherein: the acrylic monomer mixture comprises acrylic acid, styrene and methyl acrylate, and the weight ratio of acrylic acid, styrene and methyl acrylate is 1:2:0.6; the initiator is 2,2-di(tert-butylperoxide)butane; the solvent is n-butanol; the neutralizer is dimethylethanolamine; and the acid value of the anionic water-dispersible epoxy ester resin is less than 15.

[0037] The preparation method of anionic water-dispersible epoxy ester resin is as follows:

[0038] Put oleic acid modified epoxy resin and solvent into a clean reactor and stir, heat to 120-130°C, add acrylic monomer mixture and initiator, react at 120-130°C for 3-4h to obtain acrylic modified epoxy resin, then cool to 60-80°C, add neutralizer and stir to react for 45-75min to obtain anionic water-dispersible epoxy ester resin.

[0039] Preferably, the oleic acid-modified epoxy resin comprises 13-15 parts by weight of bisphenol A epoxy resin, 0.02-0.05 parts by weight of a catalyst and 30-35 parts by weight of oleic acid; the bisphenol A epoxy resin is E12; the catalyst is zinc oxide; the oleic acid is dehydrated ricinoleic acid and linoleic acid, and the weight ratio of dehydrated ricinoleic acid to linoleic acid is 7:3; the acid value of the oleic acid-modified epoxy resin is less than 20.

[0040] The preparation method of oleic acid modified epoxy resin is as follows:

[0041] Add bisphenol A epoxy resin and catalyst into a clean reactor and stir, heat to 140-150°C, add oleic acid, and carry out esterification reaction at 140-150°C for 3-4 hours to obtain oleic acid-modified epoxy resin.

[0042] Through the above technical solution, in the present invention:

[0043] (1) The ring opening of epoxy resin can be achieved by esterification reaction between dehydrated ricinoleic acid and linoleic acid and small molecule epoxy resin. The introduction of dehydrated ricinoleic acid and linoleic acid can increase the molecular chain length of epoxy resin. At the same time, water-resistant functional groups such as chain-extended polycarbonate and carboxyl groups are introduced to improve the water resistance of epoxy resin. At the same time, when the anionic water-dispersible epoxy ester resin of the present invention is used, the double bonds on the linoleic acid can be oxidatively cross-linked under the action of a drying agent, which is beneficial to further improve the physical properties of the enamel coating.

[0044] (2) The epoxy resin modified with dehydrated castoric acid and linoleic acid is copolymerized with acrylic acid monomers to block or graft acrylic acid onto the epoxy resin, thereby adding functional groups such as urea, silane, and titanate that improve adhesion. After some hydrophilic groups in acrylic acid are introduced into the epoxy resin molecular chain, the epoxy resin is made to contain both hydrophilic groups and lipophilic groups through reaction with a neutralizer. The epoxy resin with hydrophilic and lipophilic groups can obtain self-emulsification properties. At the same time, the excess neutralizer can provide a weakly alkaline workpiece environment in the system, which helps to increase the anti-rust effect of the pretreatment agent and synergistically facilitates the application of the modified epoxy resin in the pretreatment agent.

[0045] (3) The type and dosage of the degreasing agent used can not only increase the solubility of the anionic water-dispersible epoxy ester resin in pure water, but also cooperate with the anionic water-dispersible epoxy ester resin to assist in degreasing the workpiece.

[0046] (4) The acid-base regulator used and its dosage can provide a weak alkaline environment to promote and enhance the degreasing effect; at the same time, the weak alkaline conditions and the cross-linking reaction between the resin and the metal at high temperature can play a synergistic anti-corrosion role on the surface of the substrate, ensuring that the workpiece will not rust within 24 hours after the previous treatment.

[0047] In summary, the anionic water-dispersible epoxy ester resin used in the two-in-one degreasing and rust-proofing water-free zero-emission pretreatment agent has good self-emulsifying properties. The self-emulsifying property can effectively remove the oil stains on the surface of the workpiece. At the same time, the strong polar functional groups formed by the elements Si, S, N, etc. contained in the resin are entangled and embedded with the main resin of the enamel coating to achieve the effect of improving the adhesion, corrosion resistance and impact resistance of the coating.

[0048] According to the second aspect of the present invention, a two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention is used in enamel. The above-mentioned two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention is put into an enamel pretreatment tank to perform degreasing and rust prevention treatment on the workpiece. The enamel pretreatment tank is a two-in-one degreasing and rust prevention tank and the number is 1 to 3.

[0049] Specifically, when the two-in-one degreasing and rust-proofing water-free and zero-emission pretreatment agent is applied to enamel pretreatment, one enamel pretreatment tank can meet the working requirements of degreasing and rust-proofing and water-free and zero-emission pretreatment; but considering the spraying time and length of the production line, the enamel pretreatment tanks can be selectively set to 1 to 3, and the 1 to 3 enamel pretreatment tanks are all filled with the two-in-one degreasing and rust-proofing water-free and zero-emission pretreatment agent of the present invention.

[0050] Through the above technical scheme, the degreasing and rust-proof two-in-one water-free and zero-emission pretreatment agent of the present invention is used to treat the workpiece before enameling. There is no wastewater discharge in the pretreatment process, and the surface after the pretreatment is enameled. The adhesion of the enamel can reach level 0, the workpiece will not rust within 24 hours of storage, and the workpiece will be subjected to a 50kg frontal impact test without cracks or falling off.

[0051] Embodiment 1:

[0052] A two-in-one degreasing and rust-proofing water-free zero-emission pretreatment agent, the preparation method is as follows:

[0053] Add anionic water-dispersible epoxy ester resin and degreasing agent into a clean reactor and stir, then add acid-base regulator and stir evenly, finally add pure water and stir for 30-60 minutes to obtain a two-in-one degreasing and rust-proofing water-free zero-emission pretreatment agent.

[0054] The preparation method of anionic water-dispersible epoxy ester resin is as follows:

[0055] Put oleic acid modified epoxy resin and solvent into a clean reactor and stir, heat to 120-130°C, add acrylic monomer mixture and initiator, react at 120-130°C for 3-4h to obtain acrylic modified epoxy resin, then cool to 60-80°C, add neutralizer and stir to react for 45-75min to obtain anionic water-dispersible epoxy ester resin.

[0056] The preparation method of oleic acid modified epoxy resin is as follows:

[0057] Add bisphenol A epoxy resin and catalyst into a clean reactor and stir, heat to 140-150°C, add oleic acid, and carry out esterification reaction at 140-150°C for 3-4 hours to obtain oleic acid-modified epoxy resin.

[0058] Among them: in parts by weight: the two-in-one degreasing and rust-proof water-free zero-emission pretreatment agent includes 5 parts by weight of anionic water-dispersible epoxy ester resin, 1 part by weight of acid-base regulator, 3 parts by weight of degreasing agent and 83 parts by weight of pure water; among them: the acid-base regulator is dimethylethanolamine; the degreasing agent is ethylene glycol monobutyl ether.

[0059] The anionic water-dispersible epoxy ester resin includes 40 parts by weight of oleic acid-modified epoxy resin, 10 parts by weight of solvent, 0.3 parts by weight of initiator, 3.6 parts by weight of acrylic monomer mixture and 1.6 parts by weight of neutralizer; wherein: the acrylic monomer mixture includes acrylic acid, styrene and methyl acrylate, and the weight ratio of acrylic acid, styrene and methyl acrylate is 1:2:0.6; the initiator is 2,2-di(tert-butylperoxy)butane; the solvent is n-butanol; the neutralizer is dimethylethanolamine; the acid value of the anionic water-dispersible epoxy ester resin is less than 15.

[0060] The oleic acid modified epoxy resin includes 13 parts by weight of bisphenol A epoxy resin, 0.02 parts by weight of a catalyst and 30 parts by weight of oleic acid; the bisphenol A epoxy resin is E12; the catalyst is zinc oxide; the oleic acid is dehydrated ricinoleic acid and linoleic acid, and the weight ratio of dehydrated ricinoleic acid to linoleic acid is 7:3; the acid value of the oleic acid modified epoxy resin is less than 20.

[0061] The pH value of the obtained degreasing and rust-proofing two-in-one water-free and zero-emission pre-treatment agent is 9.5, and the solid content is 0.25%.

[0062] Embodiment 2:

[0063] Different from Example 1, this embodiment adopts: wherein: in parts by weight: the two-in-one degreasing and rust-proof water-free and zero-emission pretreatment agent includes 10 parts by weight of anionic water-dispersible epoxy ester resin, 1.5 parts by weight of acid-base regulator, 5 parts by weight of degreasing agent and 91 parts by weight of pure water; wherein: the acid-base regulator is dimethylethanolamine, ethanolamine and triethanolamine; the degreasing agent is ethylene glycol monobutyl ether, propylene glycol methyl ether and n-butanol.

[0064] The anionic water-dispersible epoxy ester resin includes 45 parts by weight of oleic acid-modified epoxy resin, 12 parts by weight of solvent, 0.5 parts by weight of initiator, 4 parts by weight of acrylic monomer mixture and 1.8 parts by weight of neutralizer; wherein: the acrylic monomer mixture includes acrylic acid, styrene and methyl acrylate, and the weight ratio of acrylic acid, styrene and methyl acrylate is 1:2:0.6; the initiator is 2,2-di(tert-butylperoxy)butane; the solvent is n-butanol; the neutralizer is dimethylethanolamine; the acid value of the anionic water-dispersible epoxy ester resin is less than 15.

[0065] The oleic acid modified epoxy resin comprises 15 parts by weight of bisphenol A epoxy resin, 0.05 parts by weight of a catalyst and 35 parts by weight of oleic acid; the bisphenol A epoxy resin is E12; the catalyst is zinc oxide; the oleic acid is dehydrated ricinoleic acid and linoleic acid, and the weight ratio of dehydrated ricinoleic acid to linoleic acid is 7:3; the acid value of the oleic acid modified epoxy resin is less than 20.

[0066] The pH value of the obtained degreasing and rust-proofing two-in-one water-free and zero-emission pretreatment agent is 9.1, and the solid content is 0.23%.

[0067] Embodiment 3:

[0068] Different from Example 1, this embodiment adopts: wherein: in parts by weight: the two-in-one degreasing and rust-proof water-free and zero-emission pretreatment agent includes 7 parts by weight of anionic water-dispersible epoxy ester resin, 1.2 parts by weight of acid-base regulator, 4 parts by weight of degreasing agent and 87 parts by weight of pure water; wherein: the acid-base regulator is dimethylethanolamine and ethanolamine; the degreasing agent is propylene glycol methyl ether and n-butanol.

[0069] The anionic water-dispersible epoxy ester resin includes 43 parts by weight of oleic acid-modified epoxy resin, 11 parts by weight of solvent, 0.4 parts by weight of initiator, 3.8 parts by weight of acrylic monomer mixture and 1.7 parts by weight of neutralizer; wherein: the acrylic monomer mixture includes acrylic acid, styrene and methyl acrylate, and the weight ratio of acrylic acid, styrene and methyl acrylate is 1:2:0.6; the initiator is 2,2-di(tert-butylperoxy)butane; the solvent is n-butanol; the neutralizer is dimethylethanolamine; the acid value of the anionic water-dispersible epoxy ester resin is less than 15.

[0070] The oleic acid modified epoxy resin includes 14 parts by weight of bisphenol A epoxy resin, 0.04 parts by weight of a catalyst and 33 parts by weight of oleic acid; the bisphenol A epoxy resin is E12; the catalyst is zinc oxide; the oleic acid is dehydrated ricinoleic acid and linoleic acid, and the weight ratio of dehydrated ricinoleic acid to linoleic acid is 7:3; the acid value of the oleic acid modified epoxy resin is less than 20.

[0071] The obtained degreasing and rust-proofing two-in-one water-free and zero-emission pre-treatment agent has a pH value of 9.0 and a solid content of 0.20%.

[0072] The degreasing and rust-proofing two-in-one water-free and zero-emission pretreatment agents prepared in Example 1, Example 2 and Example 3 were put into an enamel pretreatment tank, and the test panels were subjected to degreasing and rust-proofing treatment, and then the pretreated test panels were subjected to enamel treatment and tested:

[0073] The enameling steps are as follows:

[0074] Surface treatment: The test plate was pretreated with a two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention to obtain a pretreated test plate.

[0075] Enameling step: The test panel is enameled to obtain a test panel with an enamel protective layer.

[0076] The test panels with enamel protective layer were tested and the test results are shown in Table 1.

[0077] Table 1

[0078] Test items Example 1 Example 2 Example 3 Enamel layer appearance Flat and smooth Flat and smooth Flat and smooth Adhesion (cross-hatch method), grade 0 0 0 50kg positive impact No cracks or peeling No cracks or peeling No cracks or peeling Natural storage anti-rust effect Rust-free within 24 hours Rust-free within 24 hours Rust-free within 24 hours

[0079] Through the test of the enamel protective layer of the test plates of Example 1, Example 2 and Example 3, it can be known that the two-in-one water-free zero-emission pretreatment agent for degreasing and rust prevention of the present invention is applied to enamel pretreatment, (1) it can make the overall process flow of enamel pretreatment only need one to three tanks, and no water washing is required after the pretreatment is completed to achieve the effect of surface degreasing and rust prevention. At the same time, the residual pretreatment agent does not affect the appearance of the enamel, and does not affect the various test results of the enamel, such as the adhesion test of the enamel can reach level 0; (2) compared with the traditional enamel pretreatment process, it saves water and electricity resources, reduces emissions, and reduces the health risks to users; (3) it solves the problem of rust recurrence due to line shutdown or poor cleaning; (4) there is no cracking or falling off under the positive impact of a 50kg drop hammer.

[0080] In summary, through the technical solution of the present invention, the two-in-one water-free and zero-emission pretreatment agent for degreasing and rust prevention improves the quality of pretreatment, saves water and electricity resources, reduces emissions, and reduces health risks to users compared with the traditional enamel pretreatment process.

[0081] Finally, it should be noted that the above-described embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some or all of the technical features thereof may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A two-in-one degreasing and rust-proofing water-free zero-emission pretreatment agent, characterized by: In parts by weight: comprising 5-10 parts by weight of anionic water-dispersible epoxy ester resin, 1-1.5 parts by weight of acid-base regulator, 3-5 parts by weight of degreasing agent and 83.5-91 parts by weight of pure water; The pH value of the two-in-one water-free, zero-emission pre-treatment agent for degreasing and rust prevention is 8-11, and the solid content is 0.03-0.3%.

2. The degreasing and rust-proofing two-in-one water-free and zero-emission pretreatment agent according to claim 1, characterized in that: The preparation method of the two-in-one water-free and zero-emission pretreatment agent for degreasing and rust prevention is as follows: Add anionic water-dispersible epoxy ester resin and degreasing agent into a clean reactor and stir, then add acid-base regulator and stir evenly, finally add pure water and stir for 30-60 minutes to obtain a two-in-one degreasing and rust-proofing water-free zero-emission pretreatment agent.

3. The degreasing and rust-proofing two-in-one water-free and zero-emission pretreatment agent according to claim 1, characterized in that: The acid-base regulator is one or more of dimethylethanolamine, ethanolamine and triethanolamine; The degreasing agent is one or more of ethylene glycol monobutyl ether, propylene glycol methyl ether and n-butanol.

4. The degreasing and rust-proofing two-in-one water-free and zero-emission pretreatment agent according to claim 1, characterized in that: The anionic water-dispersible epoxy ester resin comprises 40-45 parts by weight of oleic acid-modified epoxy resin, 10-12 parts by weight of solvent, 0.3-0.5 parts by weight of initiator, 3.6-4 parts by weight of acrylic monomer mixture and 1.6-1.8 parts by weight of neutralizer; the acid value of the anionic water-dispersible epoxy ester resin is less than 15.

5. The degreasing and rust-proof two-in-one water-free and zero-emission pretreatment agent according to claim 4 is characterized by: The preparation method of anionic water-dispersible epoxy ester resin is as follows: Put oleic acid modified epoxy resin and solvent into a clean reactor and stir, heat to 120-130°C, add acrylic monomer mixture and initiator, react at 120-130°C for 3-4h to obtain acrylic modified epoxy resin, then cool to 60-80°C, add neutralizer and stir to react for 45-75min to obtain anionic water-dispersible epoxy ester resin.

6. The degreasing and rust-proof two-in-one water-free and zero-emission pretreatment agent according to claim 4, characterized in that: The acrylic monomer mixture includes acrylic acid, styrene and methyl acrylate, and the weight ratio of acrylic acid, styrene and methyl acrylate is 1:2:0.6; The initiator is 2,2-di(tert-butylperoxy)butane; The solvent is n-butanol; The neutralizing agent is dimethylethanolamine.

7. The degreasing and rust-proofing two-in-one water-free and zero-emission pretreatment agent according to claim 4 is characterized by: The oleic acid-modified epoxy resin comprises 13-15 parts by weight of bisphenol A epoxy resin, 0.02-0.05 parts by weight of a catalyst and 30-35 parts by weight of oleic acid; The acid value of the oleic acid-modified epoxy resin is less than 20.

8. The degreasing and rust-proof two-in-one water-free and zero-emission pretreatment agent according to claim 7, characterized in that: The preparation method of oleic acid modified epoxy resin is as follows: Add bisphenol A epoxy resin and catalyst into a clean reactor and stir, heat to 140-150°C, add oleic acid, and carry out esterification reaction at 140-150°C for 3-4 hours to obtain oleic acid-modified epoxy resin.

9. The degreasing and rust-proof two-in-one water-free and zero-emission pretreatment agent according to claim 7, characterized in that: Bisphenol A epoxy resin is E12; The catalyst is zinc oxide; The oleic acid is dehydrated ricinoleic acid and linoleic acid, and the weight ratio of the dehydrated ricinoleic acid to the linoleic acid is 7:

3.

10. Application of a two-in-one water-free, zero-emission pretreatment agent for degreasing and rust prevention in enamel, characterized in that: The degreasing and rust-proofing two-in-one water-free and zero-emission pretreatment agent described in any one of claims 1-9 is put into an enamel pretreatment tank to perform degreasing and rust-proofing treatment on the workpiece. The enamel pretreatment tank is a degreasing and rust-proofing two-in-one tank and the number is 1-3.