Antioxidant water-based paint and process for its preparation
By designing a multifunctional additive, hindered phenolic antioxidant units and phosphorus phenanthrene flame retardant units are covalently bonded, solving the problem of insufficient antioxidant and flame retardant properties of water-based paints, achieving long-lasting antioxidant and flame retardant properties of the paint, and improving the mechanical properties of the paint film.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ANHUI MINGSHIDA NEW MATERIAL CO LTD
- Filing Date
- 2025-11-06
- Publication Date
- 2026-06-05
AI Technical Summary
Existing water-based paints are inferior to traditional solvent-based paints in terms of antioxidant and flame retardant properties. Furthermore, small molecule additives are prone to migration and volatilization, and physically blended additives suffer from poor compatibility and functional degradation, which affect the performance of the paint film.
A multifunctional additive was developed by introducing a terminal double bond into the 4-hydroxybenzaldehyde molecule via a Williamson ether synthesis reaction to form a Schiff base intermediate. Then, a nucleophilic addition reaction was performed using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to link 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid with 3-bromopropylamine, constructing a hindered phenolic structure. This achieved covalent bonding between the hindered phenolic antioxidant unit and the phosphaphenanthrene flame-retardant unit, resulting in a multifunctional additive integrating antioxidant and flame-retardant functions.
It achieves long-lasting antioxidant and flame-retardant properties of the paint, avoids the migration and volatilization problems of small molecule additives, ensures the long-term effectiveness of the function, and improves the mechanical properties and functional synergy of the paint film through covalent bonding.
Smart Images
Figure IMAGE_D5B672C1-417A-42E4-B8A3-35167848C93C
Abstract
Description
Technical Field
[0001] This invention belongs to the field of paint technology, specifically relating to an antioxidant water-based paint and its preparation process. Background Technology
[0002] Currently, water-based paints are widely used due to their environmentally friendly characteristics, but in terms of durability, especially in terms of anti-oxidation and flame retardancy, they are often inferior to traditional solvent-based paints.
[0003] In existing technologies, to improve the oxidation resistance of water-based paints, small-molecule antioxidants, such as hindered phenolic compounds (e.g., antioxidant 1010), are typically added directly. However, these small-molecule additives are prone to migration, volatilization, or leaching during paint storage and use, causing their functionality to rapidly decline over time and failing to provide long-term effective protection. Similarly, flame retardants added through physical blending to achieve flame retardant properties also suffer from poor compatibility with the matrix and uneven dispersion, potentially affecting the overall performance of the paint film. Furthermore, physical blending makes it difficult to achieve a synergistic effect between oxidation resistance and flame retardancy. In addition, simply compounding functional additives may negatively impact the mechanical properties of the paint film.
[0004] Therefore, developing a novel additive and corresponding preparation process that can stably exist in the paint film and simultaneously and effectively impart excellent antioxidant and flame retardant properties to water-based paints without impairing their physical and mechanical properties has become a pressing technical problem to be solved in this field. Summary of the Invention
[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide an antioxidant water-based paint and its preparation process.
[0006] The objective of this invention can be achieved through the following technical solutions:
[0007] A preparation process for an antioxidant water-based paint includes the following steps:
[0008] Deionized water, defoamer, water-based acrylic emulsion, multifunctional additive, film-forming aid, leveling agent, and nano silica are mixed and stirred continuously for 20-30 minutes. Then, ammonium persulfate aqueous solution is added and stirred for 10-15 minutes. After filtration, the product is discharged to obtain water-based paint.
[0009] In a more optimized manner, the raw materials for preparing the water-based paint include the following components: by weight, 15-18 parts deionized water, 0.2-0.5 parts defoamer, 45-50 parts water-based acrylic emulsion, 10-12 parts multifunctional additive, 3-6 parts film-forming aid, 0.1-0.2 parts leveling agent, 2-3 parts nano-silica, and 4-5 parts ammonium persulfate aqueous solution; wherein the concentration of the ammonium persulfate aqueous solution is 8 wt%.
[0010] In a more optimized manner, the preparation process of the multifunctional additive is as follows:
[0011] S1: Mix 4-hydroxybenzaldehyde, 3-butenyl bromide, anhydrous ethanol and potassium carbonate, raise the temperature to 80-90℃, reflux for 24h, and then perform post-treatment to obtain product A.
[0012] S2: Mix product A, 3-amino-1,2,4-triazole and anhydrous ethanol, adjust the pH to neutral, raise the temperature to 80-90℃, reflux for 24h, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continue the reaction for 10-12h, after the reaction is completed, cool to room temperature, and filter under vacuum to obtain product B;
[0013] S3: Under a protective atmosphere, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, triethylamine and anhydrous dichloromethane were mixed and stirred until homogeneous. Then, 3-bromopropylamine and N,N'-diisopropylcarbodiimide were added and stirred at room temperature for 2-3 hours. After post-treatment, product C was obtained.
[0014] S4: Mix product C, product B, potassium carbonate, and N,N-dimethylformamide, raise the temperature to 60-80℃, stir and react for 3-4 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry to obtain a multifunctional additive.
[0015] In this scheme, a terminal double bond is first introduced into the 4-hydroxybenzaldehyde molecule via a Williamson ether synthesis reaction to obtain product A. Subsequently, product A condenses with 3-amino-1,2,4-triazole to form a Schiff base intermediate, and a nucleophilic addition is performed on the C=N double bond of this intermediate using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to introduce a phosphaphenanthrene flame-retardant structure, yielding product B. Next, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid is linked to 3-bromopropylamine via an amidation reaction to construct a hindered phenolic structure with a terminal bromine, yielding product C. Finally, the hindered phenolic antioxidant unit and the phosphorus-containing flame-retardant unit are covalently bonded through a nucleophilic substitution reaction between the bromine terminus of product C and the nitrogen atom on the triazole ring of product B, resulting in a multifunctional additive with both antioxidant and flame-retardant functions. The structure of the multifunctional additive is shown below:
[0016]
[0017] In a more optimized manner, the raw materials for preparing product A include the following components: by weight, 10-12 parts of 4-hydroxybenzaldehyde, 12-13 parts of 3-butenyl bromide, 80-100 parts of anhydrous ethanol, and 8-10 parts of potassium carbonate.
[0018] In a more optimized manner, the raw materials for preparing product B include the following components: by weight, 10-12 parts of product A, 5-6 parts of 3-amino-1,2,4-triazole, 100-120 parts of anhydrous ethanol, and 11-12 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
[0019] In a more optimized manner, the raw materials for preparing product C include the following components: by weight, 10-12 parts of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, 2-3 parts of triethylamine, 80-100 parts of anhydrous dichloromethane, 4-5 parts of 3-bromopropylamine, and 5-6 parts of N,N'-diisopropylcarbodiimide.
[0020] In a more optimized manner, the raw materials for preparing the multifunctional additive include the following components: by weight, 10-12 parts of product C, 14-15 parts of product B, 2-3 parts of potassium carbonate, and 80-100 parts of N,N-dimethylformamide.
[0021] The beneficial effects of this invention are:
[0022] This invention provides a preparation process for an antioxidant water-based paint. By designing a multifunctional additive containing cross-linkable double bonds, a synergistic improvement in the paint's antioxidant properties, flame retardancy, and film durability is achieved, as detailed below:
[0023] Firstly, this invention introduces active double bonds into the multifunctional additive molecule, enabling it to covalently cross-link with the film-forming polymer during the paint film-forming process, thereby permanently anchoring it in the three-dimensional polymer network through chemical bonds. This mechanism effectively avoids the performance degradation problems caused by the migration, volatilization, or exudation of small molecule additives, ensuring the long-term effectiveness of the function.
[0024] Secondly, this invention integrates hindered phenolic antioxidant units and phosphaphenanthrene flame-retardant units into a single molecule via covalent bonds. This structure not only ensures the uniform distribution of functional components in the matrix but also promotes synergistic effects at the molecular level: the hindered phenolic units quench free radicals to inhibit oxidative degradation, while the phosphaphenanthrene units exert their flame-retardant effects through gas-phase and condensed-phase mechanisms. The two are linked by stable chemical bonds, avoiding potential mutual interference during physical blending and achieving synergistic enhancement of functions.
[0025] Thirdly, the multifunctional additive of this invention participates in the cross-linking reaction through its terminal double bonds, becoming an active cross-linking point in the polymer network. This effectively increases the cross-linking density of the paint film, making its structure more compact and complete. Therefore, while imparting antioxidant and flame-retardant functions to the paint film, this additive not only does not weaken its mechanical properties but also improves certain physical and mechanical properties. Detailed Implementation
[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0027] Example 1: A preparation process for an antioxidant water-based paint, comprising the following steps:
[0028] Mix 15 parts deionized water, 0.2 parts defoamer (BYK-071), 45 parts water-based acrylic emulsion, 10 parts multifunctional additive, 3 parts film-forming aid (propylene glycol film-forming agent), 0.1 parts leveling agent (BYK-346), and 2 parts nano silica, and stir continuously for 20 minutes. Then add 4 parts ammonium persulfate aqueous solution (8wt%), stir for 10 minutes, filter, and discharge to obtain water-based paint.
[0029] The preparation process of the multifunctional additive is as follows:
[0030] S1: Mix 10 parts of 4-hydroxybenzaldehyde, 12 parts of 3-butenyl bromide, 80 parts of anhydrous ethanol and 8 parts of potassium carbonate, raise the temperature to 80℃, reflux for 24 h, and then perform post-treatment to obtain product A.
[0031] S2: Mix 10 parts of product A, 5 parts of 3-amino-1,2,4-triazole and 100 parts of anhydrous ethanol, adjust the pH to neutral, raise the temperature to 80℃, and reflux for 24 h. Then add 11 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and continue the reaction for 10 h. After the reaction is completed, cool to room temperature, and filter under vacuum to obtain product B.
[0032] S3: Under a protective atmosphere, 10 parts of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, 2 parts of triethylamine and 80 parts of anhydrous dichloromethane were mixed and stirred until homogeneous. Then, 4 parts of 3-bromopropylamine and 5 parts of N,N'-diisopropylcarbodiimide were added and stirred at room temperature for 2 hours. After post-treatment, product C was obtained.
[0033] S4: Mix 10 parts of product C, 14 parts of product B, 2 parts of potassium carbonate, and 80 parts of N,N-dimethylformamide, raise the temperature to 60°C, stir and react for 3 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry to obtain a multifunctional additive.
[0034] Example 2: A preparation process for an antioxidant water-based paint, comprising the following steps:
[0035] Mix 18 parts deionized water, 0.5 parts defoamer (BYK-071), 50 parts water-based acrylic emulsion, 12 parts multifunctional additive, 6 parts film-forming aid (propylene glycol film-forming agent), 0.2 parts leveling agent (BYK-346), and 3 parts nano silica, and stir continuously for 30 minutes. Then add 5 parts ammonium persulfate aqueous solution (8wt%), stir for 15 minutes, filter, and discharge to obtain water-based paint.
[0036] The preparation process of the multifunctional additive is as follows:
[0037] S1: Mix 12 parts of 4-hydroxybenzaldehyde, 13 parts of 3-butenyl bromide, 100 parts of anhydrous ethanol and 10 parts of potassium carbonate, raise the temperature to 90℃, reflux for 24 h, and then perform post-treatment to obtain product A.
[0038] S2: Mix 12 parts of product A, 6 parts of 3-amino-1,2,4-triazole and 120 parts of anhydrous ethanol, adjust the pH to neutral, raise the temperature to 90℃, and reflux for 24 h. Then add 12 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and continue the reaction for 12 h. After the reaction is completed, cool to room temperature, and filter under vacuum to obtain product B.
[0039] S3: Under a protective atmosphere, 12 parts of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, 3 parts of triethylamine and 100 parts of anhydrous dichloromethane were mixed and stirred until homogeneous. Then, 5 parts of 3-bromopropylamine and 6 parts of N,N'-diisopropylcarbodiimide were added and stirred at room temperature for 3 hours. After post-treatment, product C was obtained.
[0040] S4: Mix 12 parts of product C, 15 parts of product B, 3 parts of potassium carbonate, and 100 parts of N,N-dimethylformamide, raise the temperature to 80°C, stir and react for 4 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry to obtain a multifunctional additive.
[0041] Example 3: A preparation process for an antioxidant water-based paint, comprising the following steps:
[0042] 16.5 parts deionized water, 0.35 parts defoamer (BYK-071), 47.5 parts water-based acrylic emulsion, 11 parts multifunctional additive, 4.5 parts film-forming aid (propylene glycol film-forming agent), 0.15 parts leveling agent (BYK-346), and 2.5 parts nano silica were mixed and stirred continuously for 25 minutes. Then, 4.5 parts ammonium persulfate aqueous solution (8 wt%) were added and stirred for 12.5 minutes. The mixture was filtered and discharged to obtain water-based paint.
[0043] The preparation process of the multifunctional additive is as follows:
[0044] S1: Mix 11 parts of 4-hydroxybenzaldehyde, 12.5 parts of 3-butenyl bromide, 90 parts of anhydrous ethanol and 9 parts of potassium carbonate, raise the temperature to 85℃, reflux for 24 h, and then perform post-treatment to obtain product A.
[0045] S2: Mix 11 parts of product A, 5.5 parts of 3-amino-1,2,4-triazole, and 110 parts of anhydrous ethanol, adjust the pH to neutral, raise the temperature to 85°C, and reflux for 24 h. Then add 11.5 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and continue the reaction for 11 h. After the reaction is completed, cool to room temperature, and filter under vacuum to obtain product B.
[0046] S3: Under a protective atmosphere, 11 parts of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, 2.5 parts of triethylamine and 90 parts of anhydrous dichloromethane were mixed and stirred until homogeneous. Then, 4.5 parts of 3-bromopropylamine and 5.5 parts of N,N'-diisopropylcarbodiimide were added, and the mixture was stirred at room temperature for 2.5 h. After post-treatment, product C was obtained.
[0047] S4: Mix 11 parts of product C, 14.5 parts of product B, 2.5 parts of potassium carbonate, and 90 parts of N,N-dimethylformamide, raise the temperature to 70°C, stir and react for 3.5 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry to obtain a multifunctional additive.
[0048] Comparative Example 1: No multifunctional additives were added, as detailed below:
[0049] Mix 16.5 parts deionized water, 0.35 parts defoamer (BYK-071), 47.5 parts water-based acrylic emulsion, 4.5 parts film-forming aid (propylene glycol film-forming agent), 0.15 parts leveling agent (BYK-346), and 2.5 parts nano silica, and stir continuously for 25 minutes. Then add 4.5 parts ammonium persulfate aqueous solution (8wt%), stir for 12.5 minutes, filter, and discharge to obtain water-based paint.
[0050] Comparative Example 2: Antioxidant 1010 was used to replace the multifunctional additive, as detailed below:
[0051] Mix 16.5 parts deionized water, 0.35 parts defoamer (BYK-071), 47.5 parts waterborne acrylic emulsion, 11 parts antioxidant 1010, 4.5 parts film-forming aid (propylene glycol film-forming agent), 0.15 parts leveling agent (BYK-346), and 2.5 parts nano silica, and stir continuously for 25 minutes. Then add 4.5 parts ammonium persulfate aqueous solution (8wt%), stir for 12.5 minutes, filter, and discharge to obtain waterborne paint.
[0052] Testing and experimentation:
[0053] The water-based paints obtained in the examples and comparative examples were coated and cured to prepare corresponding samples, wherein the dry film thickness was 250 μm; subsequently, relevant testing tests were conducted.
[0054] (1) The limiting oxygen index of the samples obtained in the examples and comparative examples was tested using an oxygen index tester;
[0055] (2) Artificial aging resistance test (1000h) was conducted according to standard GB / T 1865.
[0056] The obtained data is shown in the table below:
[0057] project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Limiting oxygen index (%) 29.8 30.1 30.5 21.5 22.3 Artificial aging resistance test (1000h) No bubbling, no peeling, coating chalking grade 0, discoloration grade 1, gloss loss grade 1 No bubbling, no peeling, coating chalking grade 0, discoloration grade 1, gloss loss grade 1 No bubbling, no peeling, coating chalking grade 0, discoloration grade 1, gloss loss grade 1 No bubbling, no peeling, coating chalking level 2, discoloration level 3, gloss loss level 4. No bubbling, no peeling, coating chalking (level 1), discoloration (level 2), gloss loss (level 2)
[0058] Conclusion: A comparison of the test data from the examples and comparative examples shows that the antioxidant water-based paint prepared by this invention exhibits significant advantages in both flame retardancy and durability. The limiting oxygen index of all examples reached over 29.8%, significantly higher than Comparative Example 1 (21.5%) without the multifunctional additive and Comparative Example 2 (22.3%) using the traditional antioxidant 1010. This indicates that the present invention effectively improves the flame retardant performance of the paint film by introducing a multifunctional additive containing phosphorus-containing heterophenanthrene structures. After 1000 hours of artificial aging testing, none of the sample examples showed blistering or peeling, and their chalking, discoloration, and gloss loss levels were superior to Comparative Example 1, proving that the multifunctional additive can exist stably in the paint film for a long time, providing continuous and effective antioxidant protection. Compared to Comparative Example 2, which uses only small-molecule antioxidants, this invention integrates antioxidant and flame-retardant units into a single molecule through covalent bonding. This not only solves the problems of easy migration and volatilization of small-molecule additives but also achieves synergistic functional enhancement, improving the antioxidant and flame retardant properties of the paint film while ensuring its physical and mechanical properties.
[0059] In summary, this invention has successfully developed an antioxidant water-based paint with excellent comprehensive performance and long service life, which has good application value.
[0060] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0061] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.
Claims
1. A preparation process for an antioxidant water-based paint, characterized in that, Includes the following steps: Deionized water, defoamer, water-based acrylic emulsion, multifunctional additive, film-forming aid, leveling agent, and nano silica are mixed and stirred continuously for 20-30 minutes. Then, ammonium persulfate aqueous solution is added and stirred for 10-15 minutes. The mixture is filtered and discharged to obtain water-based paint. The preparation process of the multifunctional additive is as follows: S1: Mix 4-hydroxybenzaldehyde, 3-butenyl bromide, anhydrous ethanol and potassium carbonate, raise the temperature to 80-90℃, reflux for 24h, and then perform post-treatment to obtain product A. S2: Mix product A, 3-amino-1,2,4-triazole and anhydrous ethanol, adjust the pH to neutral, raise the temperature to 80-90℃, reflux for 24h, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continue the reaction for 10-12h, after the reaction is completed, cool to room temperature, and filter under vacuum to obtain product B; S3: Under a protective atmosphere, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, triethylamine and anhydrous dichloromethane were mixed and stirred until homogeneous. Then, 3-bromopropylamine and N,N'-diisopropylcarbodiimide were added and stirred at room temperature for 2-3 hours. After post-treatment, product C was obtained. S4: Mix product C, product B, potassium carbonate, and N,N-dimethylformamide, raise the temperature to 60-80℃, stir and react for 3-4 hours. After the reaction is complete, cool to room temperature, filter, wash, and dry to obtain a multifunctional additive.
2. The preparation process of an antioxidant water-based paint according to claim 1, characterized in that, The raw materials for preparing the water-based paint include the following components: by weight, 15-18 parts deionized water, 0.2-0.5 parts defoamer, 45-50 parts water-based acrylic emulsion, 10-12 parts multifunctional additive, 3-6 parts film-forming aid, 0.1-0.2 parts leveling agent, 2-3 parts nano silica, and 4-5 parts ammonium persulfate aqueous solution; wherein the concentration of the ammonium persulfate aqueous solution is 8 wt%.
3. The preparation process of an antioxidant water-based paint according to claim 1, characterized in that, The raw materials for preparing product A include the following components: by weight, 10-12 parts of 4-hydroxybenzaldehyde, 12-13 parts of 3-butenyl bromide, 80-100 parts of anhydrous ethanol, and 8-10 parts of potassium carbonate.
4. The preparation process of an antioxidant water-based paint according to claim 1, characterized in that, The raw materials for preparing product B include the following components: by weight, 10-12 parts of product A, 5-6 parts of 3-amino-1,2,4-triazole, 100-120 parts of anhydrous ethanol, and 11-12 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
5. The preparation process of an antioxidant water-based paint according to claim 1, characterized in that, The raw materials for preparing product C include the following components: by weight, 10-12 parts of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, 2-3 parts of triethylamine, 80-100 parts of anhydrous dichloromethane, 4-5 parts of 3-bromopropylamine, and 5-6 parts of N,N'-diisopropylcarbodiimide.
6. The preparation process of an antioxidant water-based paint according to claim 1, characterized in that, The raw materials for preparing the multifunctional additive include the following components: by weight, 10-12 parts of product C, 14-15 parts of product B, 2-3 parts of potassium carbonate, and 80-100 parts of N,N-dimethylformamide.
7. The water-based paint obtained by the preparation process of an antioxidant water-based paint according to any one of claims 1-6.