Acid-resistant epoxy self-leveling curing agent and preparation method thereof

Abstract

The present application relates to the technical field of curing agent, in particular to an acid-resistant epoxy self-leveling curing agent and a preparation method thereof. The preparation method comprises the following steps: dropping polyethylene glycol diglycidyl ether into castor oil-based polyoxyethylene ether; adding boron trifluoride ether complex, and reacting at 110 DEG C for 2-3 hours to obtain modified glycidyl ether; mixing epoxy resin with propylene glycol methyl ether, and then dropping into triethylenetetramine; after the dropping is completed, reacting for 4-6 hours, then adding the modified glycidyl ether and continuing to react for 3-4 hours; removing the propylene glycol methyl ether by vacuum distillation, and adding deionized water to obtain the curing agent. The molar ratio of polyethylene glycol diglycidyl ether to castor oil-based polyoxyethylene ether is 1:1; when the polyethylene glycol diglycidyl ether is being dropped, the stirring speed is 180 r / min in the first 20-30 drops, and then the stirring speed is adjusted to 600-900 r / min. The wear resistance and hardness of the curing agent are improved, and the cost is not increased.

Description

Technical Field

[0001] This invention relates to the field of curing agent technology, and more specifically, to an acid-resistant epoxy self-leveling curing agent and its preparation method. Background Technology

[0002] Curing agents, also known as hardeners, ripening agents, or stabilizers, are substances or mixtures that enhance or control the curing reaction. Resin curing is an irreversible process involving chemical reactions such as condensation, ring closure, addition, or catalysis, causing changes in thermosetting resins. Curing is achieved by adding curing (crosslinking) agents. Curing agents are essential additives; they are required in adhesives, coatings, and casting materials, otherwise epoxy resins cannot cure. The type of curing agent significantly affects the mechanical properties, heat resistance, water resistance, and corrosion resistance of the cured product.

[0003] Currently, epoxy curing agents on the market generally have poor acid resistance, which limits the development of epoxy flooring. In addition, the hardness of traditional self-leveling curing agents is usually 70~80D. In order to further improve their hardness, special treatment is usually required, which is costly and relatively complicated.

[0004] In view of the above, this application is hereby submitted. Summary of the Invention

[0005] The first objective of this invention is to provide a method for preparing an acid-resistant epoxy self-leveling curing agent, which is simple and easy to implement. While ensuring acid resistance, it can effectively improve the wear resistance and hardness of the curing agent without increasing the cost.

[0006] The second objective of this invention is to provide an acid-resistant epoxy self-leveling curing agent that has better wear resistance and hardness, without increasing production costs.

[0007] The embodiments of the present invention are implemented as follows:

[0008] A method for preparing an acid-resistant epoxy self-leveling curing agent includes the following steps:

[0009] S1: Slowly add polyethylene glycol diglycidyl ether to castor oil-based polyoxyethylene ether at 30~35℃;

[0010] S2: After the addition is complete, add boron trifluoride diethyl ether complex and react at 110℃ for 2-3 hours to obtain modified glycidyl ether;

[0011] S3: At 60℃, epoxy resin and propylene glycol methyl ether are mixed and slowly added dropwise to triethylenetetramine. After the addition is complete, the reaction is carried out for 4-6 hours. Then, modified glycidyl ether is added and the reaction is continued for 3-4 hours.

[0012] S4: After the reaction is complete, propylene glycol methyl ether is removed by vacuum distillation and deionized water is added to obtain an acid-resistant epoxy self-leveling curing agent.

[0013] In S1, the molar ratio of polyethylene glycol diglycidyl ether to castor oil-based polyoxyethylene ether is 1:1. When adding polyethylene glycol diglycidyl ether, the stirring speed is 180 r / min for the first 20 to 30 drops, and then the stirring speed is adjusted to 600 to 900 r / min.

[0014] We adjusted the dropping method of polyethylene glycol diglycidyl ether during the modification process of glycidyl ether, and adopted different stirring rates in stages, which is conducive to the full compatibility of polyethylene glycol diglycidyl ether and castor oil-based polyoxyethylene ether.

[0015] A slower initial stirring rate facilitates the preliminary compatibility between polyethylene glycol diglycidyl ether and castor oil-based polyoxyethylene ether, forming a stable and homogeneous mixed phase. During subsequent dropwise addition, a higher rate is maintained, which promotes thorough dispersion and contact between the two, leading to a more uniform and stable spatial structure. This is significant for further improving the uniformity of the curing agent, resulting in a more stable and homogeneous film.

[0016] Furthermore, when adding the last 5-10% of polyethylene glycol diglycidyl ether, the stirring speed is alternately switched between 300 r / min and 1200 r / min.

[0017] Furthermore, the stirring rate is switched every 5 drops.

[0018] After the spatial structure is formed, the movement of polyethylene glycol diglycidyl ether and castor oil-based polyoxyethylene ether molecules is restricted to some extent. In the later stages of the dropwise addition process, alternating the stirring rate can effectively improve the uniformity between polyethylene glycol diglycidyl ether and castor oil-based polyoxyethylene ether, promote the full transfer between them, and reduce the probability of uneven local distribution. This results in a more uniform and complete spatial structure in the final product.

[0019] Furthermore, steps S1 and S2 are performed under inert gas protection.

[0020] Furthermore, in S3, the epoxy resin is modified as follows: bisphenol A type epoxy resin is mixed with phenyl glycidyl ether, polyethylene glycol and triphenylphosphine are added, and the mixture is reacted at 130~135℃ for 4~6h.

[0021] Furthermore, the molar ratio of bisphenol A epoxy resin to phenyl glycidyl ether is 1:1.

[0022] Furthermore, the preparation of epoxy resin is carried out under the protection of an inert gas.

[0023] Furthermore, steps S3 and S4 are carried out under inert gas protection.

[0024] An acid-resistant epoxy self-leveling curing agent is prepared by the above-described method for preparing an acid-resistant epoxy self-leveling curing agent.

[0025] The beneficial effects of the technical solutions in the embodiments of the present invention include:

[0026] (1) The process is simple, the cost remains the same, and the texture uniformity of the curing agent is improved.

[0027] (2) The spatial structure formed by the curing agent is more uniform, stable and sufficient, and the hardness and wear resistance are improved to a certain extent.

[0028] In summary, the preparation method of the acid-resistant epoxy self-leveling curing agent provided in this invention is simple and easy to implement. While ensuring acid resistance, it effectively improves the wear resistance and hardness of the curing agent without increasing costs. The acid-resistant epoxy self-leveling curing agent provided in this invention has better wear resistance and hardness without increasing production costs. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0030] Therefore, the detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0031] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0032] Example 1

[0033] This embodiment provides an acid-resistant epoxy self-leveling curing agent. Its preparation method includes:

[0034] Under inert gas (nitrogen) protection, 1 mol of polyethylene glycol diglycidyl ether was slowly added dropwise to 1 mol of castor oil-based polyoxyethylene ether at 35°C. During the addition, the stirring speed was 180 r / min for the first 30 drops, and then adjusted to 900 r / min. When adding the last 5% of polyethylene glycol diglycidyl ether, the stirring speed was alternated between 300 r / min and 1200 r / min, changing the stirring speed every 5 drops of polyethylene glycol diglycidyl ether until all the polyethylene glycol diglycidyl ether was added. After the addition of polyethylene glycol diglycidyl ether was complete, 0.5 g of boron trifluoride diethyl ether complex was added, and the mixture was reacted at 110°C for 2 h to obtain the modified glycidyl ether.

[0035] Under inert gas (nitrogen) protection, 1 mol of bisphenol A epoxy resin and 1 mol of phenyl glycidyl ether were mixed at 40 °C, and 0.15 mol of polyethylene glycol and 0.6 g of triphenylphosphine were added. The mixture was reacted at 130 °C for 4 h to obtain the modified epoxy resin.

[0036] Under inert gas (nitrogen) protection at 60°C, the modified epoxy resin and propylene glycol methyl ether were mixed evenly and slowly added dropwise to triethylenetetramine. After the addition was complete, the reaction was carried out for 4 hours, followed by the addition of modified glycidyl ether, and the reaction was continued for another 3 hours. After the reaction was complete, the propylene glycol methyl ether was removed by vacuum distillation, and the mixture was diluted with deionized water to obtain a water-based epoxy self-leveling curing agent. The mass ratio of the modified epoxy resin, propylene glycol methyl ether, triethylenetetramine, modified glycidyl ether, and deionized water was 1:0.5:0.6:1.5:1.5.

[0037] Example 2

[0038] This embodiment provides an acid-resistant epoxy self-leveling curing agent. Its preparation method includes:

[0039] Under inert gas (nitrogen) protection, 1 mol of polyethylene glycol diglycidyl ether was slowly added dropwise to 1 mol of castor oil-based polyoxyethylene ether at 30 °C. During the addition, the stirring speed was 180 r / min for the first 25 drops, and then adjusted to 600 r / min. When adding the last 10% of polyethylene glycol diglycidyl ether, the stirring speed was alternated between 300 r / min and 1200 r / min, changing the stirring speed every 5 drops of polyethylene glycol diglycidyl ether until all the polyethylene glycol diglycidyl ether was added. After the addition of polyethylene glycol diglycidyl ether was complete, 0.5 g of boron trifluoride diethyl ether complex was added, and the mixture was reacted at 110 °C for 3 h to obtain the modified glycidyl ether.

[0040] Under inert gas (nitrogen) protection, 1 mol of bisphenol A epoxy resin and 1 mol of phenyl glycidyl ether were mixed at 40 °C, and 0.15 mol of polyethylene glycol and 0.6 g of triphenylphosphine were added. The mixture was reacted at 135 °C for 6 h to obtain the modified epoxy resin.

[0041] Under inert gas (nitrogen) protection at 60°C, the modified epoxy resin and propylene glycol methyl ether were mixed evenly and slowly added dropwise to triethylenetetramine. After the addition was complete, the reaction was carried out for 6 hours, followed by the addition of modified glycidyl ether, and the reaction was continued for another 4 hours. After the reaction was complete, the propylene glycol methyl ether was removed by vacuum distillation, and the mixture was diluted with deionized water to obtain a water-based epoxy self-leveling curing agent. The mass ratio of the modified epoxy resin, propylene glycol methyl ether, triethylenetetramine, modified glycidyl ether, and deionized water was 1:0.5:0.6:1.5:1.5.

[0042] Example 3

[0043] This embodiment provides an acid-resistant epoxy self-leveling curing agent. Its preparation method includes:

[0044] Under inert gas (nitrogen) protection, 1 mol of polyethylene glycol diglycidyl ether was slowly added dropwise to 1 mol of castor oil-based polyoxyethylene ether at 35°C. During the addition, the stirring speed was 180 r / min for the first 20 drops, and then adjusted to 750 r / min. When adding the last 8% of polyethylene glycol diglycidyl ether, the stirring speed was alternated between 300 r / min and 1200 r / min, changing the stirring speed every 5 drops of polyethylene glycol diglycidyl ether until all the polyethylene glycol diglycidyl ether was added. After the addition of polyethylene glycol diglycidyl ether was complete, 0.5 g of boron trifluoride diethyl ether complex was added, and the mixture was reacted at 110°C for 2.5 h to obtain the modified glycidyl ether.

[0045] Under inert gas (nitrogen) protection, 1 mol of bisphenol A type epoxy resin and 1 mol of phenyl glycidyl ether were mixed at 40 °C, and 0.15 mol of polyethylene glycol and 0.6 g of triphenylphosphine were added. The mixture was reacted at 130 °C for 5 h to obtain the modified epoxy resin.

[0046] Under inert gas (nitrogen) protection at 60°C, the modified epoxy resin and propylene glycol methyl ether were mixed evenly and slowly added dropwise to triethylenetetramine. After the addition was complete, the reaction was carried out for 5 hours, followed by the addition of modified glycidyl ether, and the reaction was continued for another 4 hours. After the reaction was complete, the propylene glycol methyl ether was removed by vacuum distillation, and the mixture was diluted with deionized water to obtain a water-based epoxy self-leveling curing agent. The mass ratio of the modified epoxy resin, propylene glycol methyl ether, triethylenetetramine, modified glycidyl ether, and deionized water was 1:0.5:0.6:1.5:1.5.

[0047] Example 4

[0048] This embodiment provides an acid-resistant epoxy self-leveling curing agent. Its preparation method includes:

[0049] Under inert gas (nitrogen) protection, 1 mol of polyethylene glycol diglycidyl ether was slowly added dropwise to 1 mol of castor oil-based polyoxyethylene ether at 35°C. During the addition, the stirring speed was 180 r / min for the first 30 drops, and then adjusted to 800 r / min. When adding the last 5% of polyethylene glycol diglycidyl ether, the stirring speed was alternated between 300 r / min and 1200 r / min, changing the stirring speed every 5 drops of polyethylene glycol diglycidyl ether until all the polyethylene glycol diglycidyl ether was added. After the addition of polyethylene glycol diglycidyl ether was complete, 0.5 g of boron trifluoride diethyl ether complex was added, and the mixture was reacted at 110°C for 3 h to obtain the modified glycidyl ether.

[0050] Under inert gas (nitrogen) protection, 1 mol of bisphenol A epoxy resin and 1 mol of phenyl glycidyl ether were mixed at 40 °C, and 0.15 mol of polyethylene glycol and 0.6 g of triphenylphosphine were added. The mixture was reacted at 130 °C for 6 h to obtain the modified epoxy resin.

[0051] Under inert gas (nitrogen) protection at 60°C, the modified epoxy resin and propylene glycol methyl ether were mixed evenly and slowly added dropwise to triethylenetetramine. After the addition was complete, the reaction was carried out for 6 hours, followed by the addition of modified glycidyl ether, and the reaction was continued for another 4 hours. After the reaction was complete, the propylene glycol methyl ether was removed by vacuum distillation, and the mixture was diluted with deionized water to obtain a water-based epoxy self-leveling curing agent. The mass ratio of the modified epoxy resin, propylene glycol methyl ether, triethylenetetramine, modified glycidyl ether, and deionized water was 1:0.5:0.6:1.5:1.5.

[0052] Example 5

[0053] This embodiment provides an acid-resistant epoxy self-leveling curing agent. Its preparation method includes:

[0054] Under inert gas (nitrogen) protection, 1 mol of polyethylene glycol diglycidyl ether was slowly added dropwise to 1 mol of castor oil-based polyoxyethylene ether at 35°C. During the addition, the stirring speed was 180 r / min for the first 30 drops, and then adjusted to 900 r / min. When adding the last 5% of polyethylene glycol diglycidyl ether, the stirring speed was alternated between 300 r / min and 1200 r / min, changing the stirring speed every 5 drops of polyethylene glycol diglycidyl ether until all the polyethylene glycol diglycidyl ether was added. After the addition of polyethylene glycol diglycidyl ether was complete, 0.5 g of boron trifluoride diethyl ether complex was added, and the mixture was reacted at 110°C for 2 h to obtain the modified glycidyl ether.

[0055] Under inert gas (nitrogen) protection, 1 mol of bisphenol A epoxy resin and 1 mol of phenyl glycidyl ether were mixed at 40 °C, and 0.15 mol of polyethylene glycol and 0.6 g of triphenylphosphine were added. The mixture was reacted at 130 °C for 4 h to obtain the modified epoxy resin.

[0056] Under inert gas (nitrogen) protection at 60°C, the modified epoxy resin and propylene glycol methyl ether were mixed evenly and slowly added dropwise to triethylenetetramine. After the addition was complete, the reaction was carried out for 4 hours, followed by the addition of modified glycidyl ether, and the reaction was continued for another 3 hours. After the reaction was complete, the propylene glycol methyl ether was removed by vacuum distillation, and the mixture was diluted with deionized water to obtain a water-based epoxy self-leveling curing agent. The mass ratio of the modified epoxy resin, propylene glycol methyl ether, triethylenetetramine, modified glycidyl ether, and deionized water was 1:0.6:0.8:1.5:1.7.

[0057] Example 6

[0058] This embodiment provides an acid-resistant epoxy self-leveling curing agent. Its preparation method includes:

[0059] Under inert gas (nitrogen) protection, 1 mol of polyethylene glycol diglycidyl ether was slowly added dropwise to 1 mol of castor oil-based polyoxyethylene ether at 35°C. During the addition, the stirring speed was 180 r / min for the first 30 drops, and then adjusted to 600 r / min. When adding the last 10% of polyethylene glycol diglycidyl ether, the stirring speed was alternated between 300 r / min and 1200 r / min, changing the stirring speed every 5 drops of polyethylene glycol diglycidyl ether until all the polyethylene glycol diglycidyl ether was added. After the addition of polyethylene glycol diglycidyl ether was complete, 0.5 g of boron trifluoride diethyl ether complex was added, and the mixture was reacted at 110°C for 2 h to obtain the modified glycidyl ether.

[0060] Under inert gas (nitrogen) protection, 1 mol of bisphenol A epoxy resin and 1 mol of phenyl glycidyl ether were mixed at 40 °C, and 0.15 mol of polyethylene glycol and 0.6 g of triphenylphosphine were added. The mixture was reacted at 135 °C for 4 h to obtain the modified epoxy resin.

[0061] Under inert gas (nitrogen) protection at 60°C, the modified epoxy resin and propylene glycol methyl ether were mixed evenly and slowly added dropwise to triethylenetetramine. After the addition was complete, the reaction was carried out for 4 hours, followed by the addition of modified glycidyl ether, and the reaction was continued for another 3 hours. After the reaction was complete, the propylene glycol methyl ether was removed by vacuum distillation, and the mixture was diluted with deionized water to obtain a water-based epoxy self-leveling curing agent. The mass ratio of the modified epoxy resin, propylene glycol methyl ether, triethylenetetramine, modified glycidyl ether, and deionized water was 0.9:0.4:0.6:1.4:1.5.

[0062] Experimental Example

[0063] The performance of the acid-resistant epoxy self-leveling curing agents prepared in Examples 1 to 6 was tested, and the test results are shown in the table below:

[0064]

[0065] Therefore, it can be seen that the curing agent prepared by the method of preparing acid-resistant epoxy self-leveling curing agent provided by the present invention, while ensuring acid resistance, wear resistance and hardness, and other properties are also stable and reliable, without changing the cost.

[0066] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing an acid-resistant epoxy self-leveling curing agent, characterized in that, The method comprises the following steps: S1: slowly drop polyethylene glycol diglycidyl ether into castor oil-based polyoxyethylene ether at 30-35℃; S2: after the dropping is completed, add boron trifluoride ether complex, and react at 110℃ for 2-3h to obtain modified glycidyl ether; S3: mix epoxy resin and propylene glycol methyl ether at 60℃, then slowly drop into triethylenetetramine, after the dropping is completed, react for 4-6h, then add the modified glycidyl ether and continue to react for 3-4h; S4: after the reaction is completed, remove propylene glycol methyl ether by distillation under reduced pressure, and add deionized water to obtain acid-resistant epoxy self-leveling curing agent; In S1, the molar ratio of polyethylene glycol diglycidyl ether to castor oil-based polyoxyethylene ether is 1:1; when the polyethylene glycol diglycidyl ether is being dropped, the stirring speed is 180r / min in the first 20-30 drops, and then the stirring speed is adjusted to 600-900r / min; When the last 5-10% of polyethylene glycol diglycidyl ether is being dropped, the stirring speed is alternately switched between 300r / min and 1200r / min; the stirring speed is switched every 5 drops; In S3, the epoxy resin is modified by mixing bisphenol A type epoxy resin with phenyl glycidyl ether, adding polyethylene glycol and triphenylphosphine, and reacting at 130-135℃ for 4-6h.

2. The method for preparing the acid-resistant epoxy self-leveling curing agent as described in claim 1, characterized in that, Steps S1 and S2 are carried out under inert gas protection.

3. The method for preparing the acid-resistant epoxy self-leveling curing agent as described in claim 1, characterized in that, The molar ratio of bisphenol A type epoxy resin to phenyl glycidyl ether is 1:

1.

4. The method for preparing the acid-resistant epoxy self-leveling curing agent as described in claim 1, characterized in that, When preparing the epoxy resin, the preparation is carried out under inert gas protection.

5. The method for preparing the acid-resistant epoxy self-leveling curing agent as described in claim 1, characterized in that, Steps S3 and S4 are carried out under inert gas protection.

6. An acid resistant epoxy self-leveling curing agent, characterized by, Prepared by the method of preparing acid-resistant epoxy self-leveling curing agent according to any one of claims 1-5.

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