EEP-containing green coating composition and preparation method thereof

Abstract

The invention relates to a green coating composition containing EEP and a preparation method thereof. The green coating composition containing EEP comprises the following components in parts by mass: 60-80 parts of organic resin, 10-40 parts of modified polyacrylate, 10-20 parts of modified titanium dioxide, 1-10 parts of an auxiliary agent, 30-50 parts of EEP and water. Wherein the modified polyacrylate is obtained by reacting alkyl acrylate, isocyanate acrylate, polyethylene glycol acrylate and N-methyldiethanolamine; the modified titanium dioxide is polyacrylic acid surface modified titanium dioxide. The compatibility of various components and matrix resin is good, the components can be crosslinked to form a stable network structure, various properties of the coating are improved, meanwhile, the environment-friendly ethyl 3-ethoxypropionate is adopted as the solvent, potential risks to the environment and human bodies are reduced, and the coating has good application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to a green coating composition containing EEP and a preparation method thereof. Background Art

[0002] At present, commonly used coatings such as acrylic coatings usually use methanol, ethyl acetate, ethanol and other substances as solvents. However, methanol is highly toxic and harmful to the human body and the environment, while ethyl acetate and ethanol have the defects of fast evaporation, difficult storage, and inconvenient construction. In addition, the above solvents are also flammable and explosive, which poses a great safety hazard. There are also coating products that use petroleum solvents and aromatic solvents, but they still have the problem of poor solubility for synthetic resins or high pollution.

[0003] In addition to the base resin, various functional fillers need to be added to coating products, such as color powder, thermal conductivity, tackifier, dielectric components, etc. However, most fillers are inorganic components with poor compatibility with the base resin. After mixing multiple components, problems such as uneven mixing, component agglomeration and precipitation are prone to occur, which seriously affects the use of coating products and also causes poor stability and insufficient strength of the coating film, making it difficult to be effective for a long time.

[0004] There is an existing technology that uses a method of organically modifying fillers to improve the compatibility of fillers with resins, but the processing process of the above method is usually complicated, and the effect of improving the stability and mechanical properties of the coating is not ideal. It is also difficult to meet the increasing requirements for additional performance (such as self-cleaning, self-repairing, etc.), and further improvement is needed.

[0005] In summary, it is urgent to develop a new technical solution to solve the problems existing in the prior art. Summary of the invention

[0006] Based on this, the present invention develops a green coating composition containing EEP and a preparation method thereof. The present invention uses modified polyacrylate obtained by reacting alkyl acrylate, acrylic isocyanate, polyethylene glycol acrylate, and N-methyldiethanolamine and polyacrylic acid modified titanium dioxide to compound. The above components have good compatibility with the matrix resin, can be cross-linked to form a stable network structure, and improve various properties of the coating. At the same time, the present invention uses green and environmentally friendly 3-ethoxyethyl propionate (EEP) as a solvent, which reduces the potential risks to the environment and human body and has good application prospects.

[0007] One object of the present invention is to provide a green coating composition containing EEP, wherein the green coating composition containing EEP comprises the following components in parts by weight:

[0008]

[0009]

[0010] water;

[0011] in,

[0012] The modified polyacrylate is obtained by reacting alkyl acrylate, acrylic isocyanate, polyethylene glycol acrylate and N-methyldiethanolamine;

[0013] The modified titanium dioxide is titanium dioxide modified with polyacrylic acid on the surface.

[0014] Furthermore, in the modified polyacrylate, the mass ratio of alkyl acrylate, acrylic isocyanate, polyethylene glycol acrylate and N-methyldiethanolamine is (3-5):1:(1-3):(1-2).

[0015] Furthermore, in the modified titanium dioxide, the mass ratio of polyacrylic acid to titanium dioxide is (0.5-5):1.

[0016] Furthermore, the auxiliary agent is selected from one or more of a wetting agent, a leveling agent, a defoaming agent, an emulsifier, a dispersant, a pH regulator, a photoinitiator, and a curing agent.

[0017] Furthermore, the organic resin includes water-based polyester resin and bisphenol epoxy acrylic resin.

[0018] Another object of the present invention is to provide a method for preparing the green coating composition containing EEP, comprising the following steps:

[0019] S1, mixing alkyl acrylate, acrylic isocyanate, polyethylene glycol acrylate and an initiator, heating and reacting under the protection of an inert gas, and then adding N-methyldiethanolamine to continue the reaction to obtain a modified polyacrylate;

[0020] S2, mixing titanium dioxide and a silane coupling agent, heating and stirring to react, mixing with acrylic acid, an initiator, and an emulsifier, heating and reacting under the protection of an inert gas, to obtain modified titanium dioxide;

[0021] S3, blending the modified polyacrylate, modified titanium dioxide and other ingredients, stirring evenly, discharging, and obtaining a product.

[0022] Furthermore, in step S1, the temperature of the heating reaction is 60-90°C.

[0023] Furthermore, in step S1, the temperature of the continued reaction is 40-70°C.

[0024] Furthermore, in step S2, the temperature of the heating and stirring reaction is 60-90°C.

[0025] Furthermore, in step S2, the temperature of the heating reaction is 50-70°C.

[0026] The present invention has the following beneficial effects:

[0027] 1. The green coating composition containing EEP provided by the present invention contains modified polyacrylate and modified titanium dioxide. The modified polyacrylate is firstly polymerized with alkyl acrylate, acrylic isocyanate and polyethylene glycol acrylate, and then further reacted with N-methyldiethanolamine through the isocyanate group, so that the modified polyacrylate obtained simultaneously introduces hydrophilic and hydrophobic groups, which is beneficial to improve the stability of the composition and avoid the phenomenon of stratification and precipitation of the product; the surface of the modified titanium dioxide of the present invention is firstly grafted with an acrylate-based silane coupling agent, and then further polymerized with acrylic acid, and the polyacrylic acid macromolecule is modified on the surface of the titanium dioxide, which effectively improves the compatibility of titanium dioxide with organic resin, makes the filler uniformly and stably dispersed in the composition, and the polyacrylic acid chain segment can be cross-linked with the hydroxyl, phenolic hydroxyl, alkoxy and other groups in the modified polyacrylate, water-based polyester resin and bisphenol A epoxy acrylic resin through chemical bonds and intermolecular forces, thereby forming a more stable network structure, thereby enhancing the mechanical strength and stability of the coating.

[0028] 2. In addition, the modified polyacrylate of the present invention has a tertiary amine group, and the modified titanium dioxide has a large number of carboxyl groups. The two can form ionic bonds for cross-linking, which not only enhances the stability and mechanical properties of the coating, but also promotes dynamic cross-linking of the components under the synergistic effect of ionic bonds and hydrogen bonds after the coating is damaged, thereby achieving a self-repairing technical effect.

[0029] 3. EEP has many advantages over traditional organic solvents. EEP has propionyl, ester, ether bonds and other groups. It is not only less volatile, but also more compatible with other components, which is beneficial to improving product stability. It does not have the risk of environmental pollution and is greener and more environmentally friendly, meeting the development needs of today's society. DETAILED DESCRIPTION

[0030] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0031] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0032] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers indicating, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0033] The organic resin in the embodiment of the present invention is a water-based polyester resin ( -4200-80) and bisphenol A epoxy acrylate resin (Sanmu 6105-80Y).

[0034] The polyethylene glycol acrylate in the embodiment of the present invention is hydroxy polyethylene glycol acrylate (HO-PEG-AC), which is purchased from Shenzhen Meiluo Technology Co., Ltd.

[0035] The auxiliary agents in the embodiment of the present invention are hydroxypropyl cellulose, photoinitiator 2959, curing agent MHG-80B and emulsifier polysorbate 80 in a mass ratio of 1:1:1:1.

[0036] The "parts" in the embodiments of the present invention refer to parts by mass.

[0037] Example 1

[0038] A green coating composition containing EEP, comprising the following components in parts by weight:

[0039]

[0040]

[0041] The preparation method of the EEP-containing composition comprises the following steps:

[0042] S1. Using toluene as solvent, butyl methacrylate, ethyl isocyanate acrylate, polyethylene glycol acrylate and ammonium persulfate in a mass ratio of 5:1:3:0.1 were mixed, reacted at 90°C for 4 hours under a nitrogen atmosphere, and then N-methyldiethanolamine (ethyl isocyanate acrylate: N-methyldiethanolamine = 1:1, m / m) was added and the reaction was continued at 70°C for 2 hours, and the solvent was removed under reduced pressure to obtain a modified polyacrylate;

[0043] S2. Using 50% (V / V) ethanol as solvent, titanium dioxide and KH570 in a mass ratio of 1:1 were mixed, stirred at 60° C. for 24 h, and filtered, washed, and dried to obtain an intermediate product;

[0044] Using deionized water as solvent, the intermediate product is mixed with acrylic acid, initiator ammonium persulfate and emulsifier OP-10 in a mass ratio of 5:15:0.1:0.3, reacted at 60° C. for 5 h under a nitrogen atmosphere, filtered, washed and dried to obtain modified titanium dioxide;

[0045] S3. Blend the modified polyacrylate, modified titanium dioxide and other ingredients according to the above mass fractions, stir evenly, and discharge to obtain a product.

[0046] Example 2

[0047] A green coating composition containing EEP, comprising the following components in parts by weight:

[0048]

[0049] The preparation method of the EEP-containing composition comprises the following steps:

[0050] S1. Using toluene as solvent, butyl methacrylate, ethyl isocyanate acrylate, polyethylene glycol acrylate and ammonium persulfate in a mass ratio of 5:1:3:0.1 were mixed, reacted at 90°C for 4 hours under a nitrogen atmosphere, and then N-methyldiethanolamine (ethyl isocyanate acrylate: N-methyldiethanolamine = 1:1, m / m) was added and the reaction was continued at 70°C for 2 hours, and the solvent was removed under reduced pressure to obtain a modified polyacrylate;

[0051] S2. Using 50% (V / V) ethanol as solvent, titanium dioxide and KH570 in a mass ratio of 1:1 were mixed, stirred at 60° C. for 24 h, and filtered, washed, and dried to obtain an intermediate product;

[0052] Using deionized water as solvent, the intermediate product is mixed with acrylic acid, initiator ammonium persulfate and emulsifier OP-10 in a mass ratio of 5:15:0.1:0.3, reacted at 60° C. for 5 h under a nitrogen atmosphere, filtered, washed and dried to obtain modified titanium dioxide;

[0053] S3. Blend the modified polyacrylate, modified titanium dioxide and other ingredients according to the above mass fractions, stir evenly, and discharge to obtain a product.

[0054] Example 3

[0055] A green coating composition containing EEP, comprising the following components in parts by weight:

[0056]

[0057] The preparation method of the EEP-containing composition comprises the following steps:

[0058] S1. Using toluene as solvent, butyl methacrylate, ethyl isocyanate acrylate, polyethylene glycol acrylate and ammonium persulfate in a mass ratio of 5:1:3:0.1 were mixed, reacted at 90°C for 4 hours under a nitrogen atmosphere, and then N-methyldiethanolamine (ethyl isocyanate acrylate: N-methyldiethanolamine = 1:1, m / m) was added and the reaction was continued at 70°C for 2 hours, and the solvent was removed under reduced pressure to obtain a modified polyacrylate;

[0059] S2. Using 50% (V / V) ethanol as solvent, titanium dioxide and KH570 in a mass ratio of 1:1 were mixed, stirred at 60° C. for 24 h, and filtered, washed, and dried to obtain an intermediate product;

[0060] Using deionized water as solvent, the intermediate product is mixed with acrylic acid, initiator ammonium persulfate and emulsifier OP-10 in a mass ratio of 5:15:0.1:0.3, reacted at 60° C. for 5 h under a nitrogen atmosphere, filtered, washed and dried to obtain modified titanium dioxide;

[0061] S3. Blend the modified polyacrylate, modified titanium dioxide and other ingredients according to the above mass fractions, stir evenly, and discharge to obtain a product.

[0062] Comparative Example 1

[0063] A coating composition, the difference between this comparative example and Example 1 is that: step S1 is modified as follows: using toluene as solvent, mixing butyl methacrylate, ethyl isocyanate acrylate, polyethylene glycol acrylate and ammonium persulfate in a mass ratio of 5:1:3:0.1, reacting at 90°C for 4h under a nitrogen atmosphere, and removing the solvent under reduced pressure to obtain a modified polyacrylate; other ingredients and preparation methods are the same as those in Example 1.

[0064] Comparative Example 2

[0065] A coating composition, the difference between this comparative example and Example 1 is that: step S2 is modified as follows: using 50% (V / V) ethanol as a solvent, titanium dioxide and KH570 in a mass ratio of 1:1 are blended, stirred and reacted at 60°C for 24 hours, filtered, washed and dried to obtain modified titanium dioxide; other ingredients and preparation methods are the same as those in Example 1.

[0066] Test Case

[0067] The coating composition samples prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests.

[0068] Test method:

[0069] The coating composition samples prepared in Examples 1-3 and Comparative Examples 1-2 were sealed in a transparent container, kept at a constant temperature of 45° C. for 30 days, and then returned to room temperature. The appearance of the samples was observed, and if no stratification or precipitation was observed, the samples were considered qualified, otherwise they were considered unqualified.

[0070] The coating composition samples prepared in Examples 1-3 and Comparative Examples 1-2 were coated on the surface of a 100 mm×100 mm metal substrate and thermally cured at 150° C. for 1 h at 700 mJ / cm 2 UV light curing was performed for 30 s to obtain a coating with a thickness of 100 μm.

[0071] Adhesion and salt spray resistance tests were carried out in accordance with HG / T 3830-2006, GB / T 9286 and other standards.

[0072] A blade was used to scratch the middle of the substrate coated with the coating composition at a pressure of 1 kg, and the width of the scratch was measured. After standing at 60°C for 6 hours, the width of the scratch was measured again and the degree of repair was calculated. If the repair rate was greater than 80%, it was judged to be qualified.

[0073] The test results are shown in Table 1.

[0074] Table 1 Performance test results

[0075]

[0076] According to Table 1, it can be concluded that the green coating composition containing EEP prepared in the embodiment of the present invention has good stability, and the coating has good adhesion and salt spray resistance, and has excellent self-repairing performance. However, in Comparative Example 1-2, modified polyacrylate or modified titanium dioxide is replaced, resulting in reduced compatibility and synergy between components, and significantly reduced stability and self-repairing performance, and the ideal performance improvement cannot be obtained. In summary, the present invention overcomes the defects of existing products and has good application prospects.

[0077] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0078] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A green coating composition containing EEP, characterized in that: The green coating composition containing EEP comprises the following components in parts by weight: water; in, The modified polyacrylate is obtained by reacting alkyl acrylate, acrylic isocyanate, polyethylene glycol acrylate and N-methyldiethanolamine; The modified titanium dioxide is titanium dioxide modified with polyacrylic acid on the surface.

2. The green coating composition containing EEP according to claim 1, characterized in that: In the modified polyacrylate, the mass ratio of alkyl acrylate, acrylic isocyanate, polyethylene glycol acrylate and N-methyldiethanolamine is (3-5):1:(1-3):(1-2).

3. The green coating composition containing EEP according to claim 1, characterized in that: In the modified titanium dioxide, the mass ratio of polyacrylic acid to titanium dioxide is (0.5-5):

1.

4. The green coating composition containing EEP according to claim 1, characterized in that: The auxiliary agent is selected from one or more of a wetting agent, a leveling agent, a defoaming agent, an emulsifier, a dispersant, a pH regulator, a photoinitiator, and a curing agent.

5. The method for preparing the green coating composition containing EEP according to any one of claims 1 to 4, characterized in that: The preparation method of the green coating composition containing EEP comprises the following steps: S1, mixing alkyl acrylate, acrylic isocyanate, polyethylene glycol acrylate and an initiator, heating and reacting under the protection of an inert gas, and then adding N-methyldiethanolamine to continue the reaction to obtain a modified polyacrylate; S2, mixing titanium dioxide and a silane coupling agent, heating and stirring to react, mixing with acrylic acid, an initiator, and an emulsifier, heating and reacting under the protection of an inert gas, to obtain modified titanium dioxide; S3, blending the modified polyacrylate, modified titanium dioxide and other ingredients, stirring evenly, discharging, and obtaining a product.

6. The method for preparing the green coating composition containing EEP according to claim 5, characterized in that: In step S1, the temperature of the heating reaction is 60-90°C.

7. The method for preparing the green coating composition containing EEP according to claim 5, characterized in that: In step S1, the temperature for continuing the reaction is 40-70°C.

8. The method for preparing the green coating composition containing EEP according to claim 5, characterized in that: In step S2, the temperature of the heating and stirring reaction is 60-90°C.

9. The method for preparing the green coating composition containing EEP according to claim 5, characterized in that: In step S2, the temperature of the heating reaction is 50-70°C.