A green coating composition containing eep and a method for preparing the same

Abstract

The present application relates to a kind of green paint compositions containing EEP and its preparation method, the green paint compositions containing EEP includes the following mass parts of ingredients: organic resin 60-80 parts, modified polyacrylate 10-40 parts, modified titanium dioxide 10-20 parts, auxiliary agent 1-10 parts, EEP 30-50 parts, water;Wherein, the modified polyacrylate is alkyl acrylate, isocyanate acrylate, polyethylene glycol acrylate, N-methyl diethanolamine reaction obtained;The modified titanium dioxide is polyacrylic acid surface modification titanium dioxide.The various components of the present application are well compatible with matrix resin, can be crosslinked to form stable network structure, improve the various properties of coating, while using green and environmentally friendly 3-ethoxy ethyl propionate as solvent, reduce the potential risk to environment and human body, with good application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, in particular to a green coating composition containing EEP and a preparation method thereof. BACKGROUND

[0002] Currently, solvents such as methanol, ethyl acetate, ethanol, etc. are usually used in common coating materials such as acrylic coating materials. However, methanol has great toxicity and causes great harm to the human body and the environment. Ethyl acetate and ethanol have the defects of fast evaporation speed, difficulty in storage, and inconvenience in construction. In addition, the above-mentioned solvents also have the problems of flammability and explosion, which have great safety hazards. There are also coating products using petroleum solvents and aromatic hydrocarbon solvents, but there are still problems of poor solubility of synthetic resins or great pollution.

[0003] In coating products, various functional fillers such as color powder, heat conductive agent, tackifier, dielectric component, etc. need to be added in addition to the base resin. However, most of the fillers are inorganic components, and the compatibility with the base resin is poor. After mixing multiple components, the problem of uneven mixing and component agglomeration and precipitation is easily caused, which seriously affects the use of the coating product and also causes the coating film to have poor stability and insufficient strength, which is difficult to last long.

[0004] There are existing technologies that use organic modification methods for fillers to improve the compatibility of the fillers with the resin. However, the above-mentioned methods have complex processing procedures, and the improvement effect on the stability and mechanical properties of the coating is not ideal, and it is also difficult to meet the increasing requirements for additional properties (such as self-cleaning, self-repairing, etc.), which need to be further improved.

[0005] In summary, there is an urgent need to develop a new technical solution to solve the problems in the prior art. SUMMARY

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

[0007] An object of the present application is to provide a green coating composition containing EEP, which comprises the following components in mass fraction:

[0008]

[0009]

[0010] water;

[0011] wherein,

[0012] the modified polyacrylate is alkyl acrylate, isocyanate acrylate, polyethylene glycol acrylate, and N-methyl diethanolamine reaction product;

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

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

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

[0016] Further, the auxiliary agent is selected from one or more of wetting agent, leveling agent, defoaming agent, emulsifying agent, dispersing agent, pH regulator, photoinitiator, and curing agent.

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

[0018] Another object of the present application is to provide a preparation method of the above-mentioned green paint composition containing EEP, comprising the following steps:

[0019] S1, mixing alkyl acrylate, isocyanate acrylate, polyethylene glycol acrylate and initiator, heating reaction under inert gas protection, then adding N-methyl diethanolamine for continuous reaction to obtain modified polyacrylate;

[0020] S2, blending titanium dioxide with silane coupling agent, heating and stirring to react, then blending with acrylic acid, initiator and emulsifying agent, heating reaction under inert gas protection to obtain modified titanium dioxide;

[0021] S3, blending the modified polyacrylate, modified titanium dioxide and other ingredients, stirring uniformly, discharging to obtain the product.

[0022] Further, in step S1, the heating reaction temperature is 60-90℃.

[0023] Further, in step S1, the continuous reaction temperature is 40-70℃.

[0024] Further, in step S2, the heating and stirring reaction temperature is 60-90℃.

[0025] Further, in step S2, the temperature of the heating reaction is 50-70℃.

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

[0027] 1. The green coating composition containing EEP provided by the present application contains modified polyacrylate and modified titanium dioxide, the modified polyacrylate is first polymerized by alkyl acrylate, isocyanate acrylate, and polyethylene glycol acrylate, and then further reacted with N-methyl diethanolamine through the isocyanate group, so that the modified polyacrylate introduced hydrophilic and hydrophobic groups at the same time, 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 in the present application is first grafted with acrylate silane coupling agent, and then further polymerized with acrylic acid, so that the polyacrylic acid macromolecule is modified on the surface of the titanium dioxide, which effectively improves the compatibility of titanium dioxide and organic resin, makes the filler uniformly and stably dispersed in the composition, and the polyacrylic acid segment can be crosslinked with the hydroxyl, phenolic hydroxyl, alkoxy and other groups in the modified polyacrylate, water-based polyester resin and bisphenol A epoxy acrylate 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 in the present application has a tertiary amine group, and the modified titanium dioxide has a large number of carboxyl groups, which can form ionic bonds for crosslinking, not only enhancing the stability and mechanical properties of the coating, but also promoting the dynamic crosslinking of the components under the synergistic action of ionic bonds and hydrogen bonds after the coating is damaged, thereby realizing the technical effect of self-repairing.

[0029] 3. EEP has many advantages compared with traditional organic solvents, EEP has propionyl, ester, ether bond and other groups, not only lower volatility, but also better compatibility with other components, which is beneficial to improve the stability of the product, and has no risk of environmental pollution, is more green and environmentally friendly, and meets the development needs of today's society. DETAILED DESCRIPTION

[0030] In order to more clearly illustrate the technical solutions of the present application, the following examples are listed. The raw materials, reactions and post-treatment methods appearing in the examples are all common raw materials on the market and technical means familiar to those skilled in the art, unless otherwise stated.

[0031] The words "preferred" and "preferably" in the application refer to embodiments of the application that can provide certain benefits under certain circumstances. However, other embodiments can also be preferred under the same or other circumstances. Additionally, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude those other embodiments from the scope of the application.

[0032] It should be understood that, except in any operating examples, or otherwise indicated herein, and that the statement of amounts of ingredients or of all numerical values in the specification and claims, are understood as being preceded by the word "about". Accordingly, unless indicated otherwise, numerical parameters in the following specification and attached claims are approximations.

[0033] The organic resin in the embodiment of the application is an aqueous polyester resin (Spectra 4200-80) and a bisphenol A epoxy acrylate resin (Miyoshi 6105-80Y) in a mass ratio of 3:1. -4200-80) and a bisphenol A epoxy acrylate resin (Miyoshi 6105-80Y) in a mass ratio of 3:1.

[0034] The polyethylene glycol acrylate in the embodiment of the application is a hydroxyl polyethylene glycol acrylate (HO-PEG-AC) available from Meilunbio Technology Co., Ltd.

[0035] The auxiliary in the embodiment of the application is hydroxypropyl cellulose, photoinitiator 2959, curing agent MGH-80B and emulsifier polysorbate-80 in a mass ratio of 1:1:1:1.

[0036] The "parts" in the embodiment of the application all refer to mass parts.

[0037] Example 1

[0038] A green coating composition containing EEP includes the following ingredients in mass parts:

[0039]

[0040]

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

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

[0043] S2, blend the intermediate product and KH570 in a mass ratio of 1:1 with 50% (V / V) ethanol as solvent, stir at 60°C for 24h, filter, wash, and dry to obtain an intermediate product;

[0044] Blend the intermediate product and KH570 in a mass ratio of 1:1 with 50% (V / V) ethanol as solvent, stir at 60°C for 24h, filter, wash, and dry to obtain an intermediate product;

[0045] S3, blend the modified polyacrylate, modified titanium dioxide, and other ingredients in the above mass fractions, stir uniformly, and discharge to obtain a product.

[0046] Example 2

[0047] A green paint composition containing EEP includes the following ingredients in mass fractions:

[0048]

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

[0050] S1, mix butyl methacrylate, isocyanate acrylate ethyl ester, polyethylene glycol acrylate, and ammonium persulfate in a mass ratio of 5:1:3:0.1 with toluene as solvent, react at 90°C under a nitrogen atmosphere for 4h, then add N-methyl diethanolamine (isocyanate acrylate ethyl ester:N-methyl diethanolamine = 1:1, m / m) and continue to react at 70°C for 2h, and remove the solvent under reduced pressure to obtain a modified polyacrylate;

[0051] S2, blend the intermediate product and KH570 in a mass ratio of 1:1 with 50% (V / V) ethanol as solvent, stir at 60°C for 24h, filter, wash, and dry to obtain an intermediate product;

[0052] Blend the intermediate product and KH570 in a mass ratio of 1:1 with 50% (V / V) ethanol as solvent, stir at 60°C for 24h, filter, wash, and dry to obtain an intermediate product;

[0053] S3, blend the modified polyacrylate, modified titanium dioxide, and other ingredients in the above mass fractions, stir uniformly, and discharge to obtain a product.

[0054] Example 3

[0055] A green paint composition containing EEP includes the following ingredients in mass fractions:

[0056]

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

[0058] S1, mixing butyl methacrylate, isocyanate acrylate ethyl, polyethylene glycol acrylate and ammonium persulfate in a mass ratio of 5:1:3:0.1 with toluene as the solvent, reacting at 90°C for 4h under nitrogen atmosphere, then adding N-methyl diethanolamine (isocyanate acrylate ethyl:N-methyl diethanolamine = 1:1, m / m) and continuing to react at 70°C for 2h, and removing the solvent under reduced pressure to obtain modified polyacrylate;

[0059] S2, blending titanium dioxide and KH570 in a mass ratio of 1:1 with 50% (V / V) ethanol as the solvent, stirring and reacting at 60°C for 24h, filtering, washing and drying to obtain an intermediate product;

[0060] blending the intermediate product with acrylic acid, initiator ammonium persulfate and emulsifier OP-10 in a mass ratio of 5:15:0.1:0.3 with deionized water as the solvent, reacting at 60°C for 5h under nitrogen atmosphere, filtering, washing and drying to obtain modified titanium dioxide;

[0061] S3, blending the modified polyacrylate, modified titanium dioxide and other components in the above mass ratio, stirring uniformly, discharging and obtaining the 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: mixing butyl methacrylate, isocyanate acrylate ethyl, polyethylene glycol acrylate and ammonium persulfate in a mass ratio of 5:1:3:0.1 with toluene as the solvent, reacting at 90°C for 4h under nitrogen atmosphere, and removing the solvent under reduced pressure to obtain modified polyacrylate; other components 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: blending titanium dioxide and KH570 in a mass ratio of 1:1 with 50% (V / V) ethanol as the solvent, stirring and reacting at 60°C for 24h, filtering, washing and drying to obtain modified titanium dioxide; other components and preparation methods are the same as those in Example 1.

[0066] Test Example

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

[0068] Test Method:

[0069] The paint composition samples prepared in Examples 1-3 and Comparative Examples 1-2 were sealed in transparent containers, and after being kept at 45℃ for 30 days, the samples were returned to room temperature. The appearance of the samples was observed, and if no delamination or precipitation occurred, the sample was determined to be qualified; otherwise, the sample was determined to be unqualified.

[0070] The paint composition samples prepared in Examples 1-3 and Comparative Examples 1-2 were coated on the surface of a 100mm x 100mm metal substrate, and cured at 150℃ for 1h, 700mJ / cm 2 UV light for 30s to obtain a 100μm-thick coating.

[0071] The adhesion and salt spray resistance were tested according to the standards of HG / T 3830-2006, GB / T 9286, etc.

[0072] A blade was used to scratch the middle of the substrate coated with the paint composition at a pressure of 1kg, and the width of the scratch was measured. After being kept at 60℃ for 6h, the width of the scratch was measured again, and the repair degree was calculated. If the repair rate was greater than 80%, the sample was determined 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 paint composition containing EEP prepared in the examples of the present application has good stability, and the adhesion and salt spray resistance of the coating are good, and the coating also has excellent self-repairing performance. In Comparative Example 1-2, the modified polyacrylate or modified titanium dioxide is replaced, which leads to a decrease in the compatibility and synergistic effect between the components, and the stability and self-repairing performance are obviously reduced, and ideal performance improvement cannot be achieved. In summary, the present application overcomes the defects of the existing products, and has a good application prospect.

[0077] It is apparent to those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, and that the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, and the scope of the present application should be defined by the appended claims rather than by the foregoing description, and all changes coming within the meaning and range of equivalency of the claims are intended to be embraced therein.

[0078] Furthermore, it should be understood that although the specification is described in terms of embodiments, not every embodiment includes every feature described. The specification can include implicit combinations of explicitly mentioned features and / or explicit combinations of implicitely mentioned features. Each embodiment depends on the explicit combinations of features and / or the implicit combinations of features made specifically within that embodiment, and each such embodiment can be combined with every other such embodiment to create further embodiments.

Claims

1. A green coating composition containing EEP, characterized in that, The green coating composition containing EEP comprises the following components by mass fraction: Water; Among them, The modified polyacrylate is an alkyl acrylate, an isocyanate acrylate, a polyethylene glycol acrylate, and a reaction product of N-methyl diethanolamine; The modified titanium dioxide is a polyacrylic acid surface modified titanium dioxide.

2. The green paint composition containing EEP according to claim 1, characterized by, In the modified polyacrylate, the mass ratio of alkyl acrylate, isocyanate acrylate, polyethylene glycol acrylate, and N-methyl diethanolamine is (3-5):1:(1-3):(1-2).

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

1.

4. The green paint composition containing EEP according to claim 1, characterized by, The auxiliary agent is selected from one or more of wetting agents, leveling agents, defoaming agents, emulsifiers, dispersants, pH regulators, photoinitiators, and curing agents.

5. A process for the preparation of 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, isocyanate acrylate, polyethylene glycol acrylate, and initiator, heating and reacting under inert gas protection, then adding N-methyl diethanolamine for continuous reaction to obtain modified polyacrylate; S2, blending titanium dioxide with silane coupling agent, heating and stirring to react, then blending with acrylic acid, initiator, and emulsifier, heating and reacting under inert gas protection to obtain modified titanium dioxide; S3, blending the modified polyacrylate, modified titanium dioxide, and other components, stirring uniformly, discharging, and obtaining the product.

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

7. The method of preparing the green paint composition containing EEP according to claim 5, characterized by, In step S1, the continuous reaction temperature is 40-70°C.

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

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

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