Modified aliphatic amine curing agent soluble in acrylate adhesives and its preparation method

Abstract

This invention relates to a modified fatty amine curing agent soluble in acrylic adhesives and its preparation method. The preparation method is as follows: polyetheramine and bismaleimide are added to a flask, a first mixed solvent is added to dissolve them, and the mixture is stirred in a water bath at a certain temperature for a period of time. Then, dodecylamine is added, and the mixture is stirred and reacted again at the above temperature for another period of time. Then, a second mixed solvent is added to achieve a certain solid content, and the mixture is stirred evenly to obtain the modified fatty amine curing agent. The mixture is then bottled, sealed, and refrigerated. The modified fatty amine curing agent soluble in acrylic adhesives of this invention has good high-temperature resistance, low polarity, and flexibility, and also exhibits good compatibility with acrylic adhesives.

Description

[Technical Field]

[0001] This invention relates to the field of chemical materials, particularly to the field of polymer materials, and especially to a modified fatty amine curing agent soluble in acrylate adhesives and its preparation method. [Background Technology]

[0002] In the field of chemical materials, acrylic adhesives are widely used in various industries, such as automotive manufacturing, electronics, and construction, due to their excellent water resistance, environmental corrosion resistance, and colorfastness. However, as electronic products continue to develop towards multifunctionality, miniaturization, lightweighting, and / or high performance, acrylics are also incorporating certain high-temperature resistant functional groups (such as epoxy functional groups). However, there are many types of epoxy resin curing agents, mainly including polyamines, isocyanates, anhydrides, imidazoles, and polythiols. Among them, amine curing agents are the most widely used, including aliphatic polyamines, alicyclic polyamines, and low-molecular-weight polyamides. Existing commercial curing agents have many drawbacks, such as high toxicity, low reactivity, poor high-temperature resistance, high brittleness of the cured coating, and significant susceptibility to environmental humidity. Furthermore, most epoxy resin curing agents have poor solubility in acrylic adhesives, leading to uneven mixing and affecting the performance of the final product. Therefore, how to develop an aliphatic amine curing agent soluble in acrylic adhesives is a technical problem that needs to be solved in the near future. [Summary of the Invention]

[0003] The technical problem to be solved by the present invention is to avoid the shortcomings of the prior art and provide a modified fatty amine curing agent that can be dissolved in acrylic adhesive and its preparation method. The modified fatty amine curing agent prepared by the present invention has amide rings, dodecyl groups and ether bonds on its chain, so the modified fatty amine curing agent has good high temperature resistance, low polarity and flexibility, and good compatibility with acrylic adhesive.

[0004] The technical solution adopted by the present invention to solve the aforementioned technical problem is as follows:

[0005] A method for preparing a modified fatty amine curing agent soluble in acrylate adhesives is provided, comprising the following steps:

[0006] Step A: Add polyetheramine and bismaleimide to a flask, add a certain amount of the first mixed solvent, and stir in a water bath at a certain temperature of 50-100°C for a period of time until the mixed solution turns red, reddish-brown or wine red to obtain the first mixed solution; in this step A, the mass ratio of polyetheramine to bismaleimide is 100:(16-83);

[0007] Step B: Dodecylamine is then added to the first mixed solution from Step A, and the mixture is stirred and reacted for another period of time under the above temperature conditions to obtain a second mixed solution; in this Step B, the mass ratio of dodecylamine to polyetheramine is (0.9~4.5):100;

[0008] Step C: Add the second mixed solvent to the second mixed solution in step B to make its solid content reach a certain value, stir evenly, and you will get a modified fatty amine curing agent that can be dissolved in acrylic ester glue. After bottling, seal and refrigerate.

[0009] In steps A and C, both the first and second mixed solvents contain isopropanol. In steps A and C, both the first and second mixed solvents also contain ethyl acetate. The mass ratio of isopropanol to ethyl acetate is (0.5–1):1.

[0010] In step C, the solid content is 25% to 50%.

[0011] This invention also provides a modified fatty amine curing agent soluble in acrylate adhesives. Specifically, the modified fatty amine curing agent soluble in acrylate adhesives obtained by the above preparation method includes polyetheramine, bismaleimide, dodecylamine, and isopropanol. The mass ratio of the polyetheramine, bismaleimide, and dodecylamine is 100:(16-83):(0.9-4.5).

[0012] Compared with the prior art, the beneficial effects of the modified fatty amine curing agent soluble in acrylate adhesives and its preparation method of the present invention are as follows:

[0013] This invention introduces ether bonds and dodecylamines to increase the solubility of fatty amine curing agents, and increases the amide ring to improve the poor temperature resistance of ether bonds. Therefore, the fatty amine curing agent prepared by this invention exhibits high temperature resistance and good compatibility in acrylic adhesives. [Attached Image Description]

[0014] Figure 1 This is a summary table of the various properties of a new adhesive prepared using the modified fatty amine curing agent that is soluble in acrylate adhesives, prepared in Example 1 of this invention.

[0015] Figure 2 This is a summary table of the various properties of a new adhesive prepared using the modified fatty amine curing agent that is soluble in acrylate adhesive prepared in Example 2 of this invention.

[0016] Figure 3 This is a summary table of the various properties of a new adhesive prepared using the modified fatty amine curing agent that is soluble in acrylate adhesives, prepared in Example 3 of this invention.

Detailed Implementation Methods

[0017] The present invention will now be described in further detail with reference to the accompanying drawings.

[0018] A method for preparing a modified fatty amine curing agent soluble in acrylate adhesives, comprising the following steps:

[0019] Step A: Add polyetheramine and bismaleimide to a four-necked flask, typically equipped with a reflux condenser, a constant-pressure dropping funnel, a stirrer, and a thermometer. Add a certain amount of the first mixed solvent and stir in a water bath at a specific temperature (50–100°C, for example, 60°C). Stir and react for a period of 18–30 hours, for example, 24 hours, until the mixed solution turns red, reddish-brown, or wine-red, thus obtaining the first mixed solution. In Step A, the polyetheramine and bismaleimide… The mass ratio is 100:(16-83); the amount of the first mixed solvent is at least sufficient to completely dissolve the polyetheramine and bismaleimide. Generally, the mass ratio of the first mixed solvent to the total mass of the polyetheramine and bismaleimide is (0.8-1.1):1; the first mixed solvent is mainly a co-solvent, which plays a dissolving role and provides a reaction environment for the copolymerization of polyetheramine and bismaleimide; in order to prevent the first mixed solution from gelling, the first mixed solvent must be a mixed solvent containing isopropanol. For example, the first mixed solvent is a mixed solvent containing isopropanol and ethyl acetate. In the early stage of the reaction, using isopropanol as a co-solvent is very beneficial for the dissolution of amine substances and prevents the first mixed solution from gelling; in the first mixed solution, the mass ratio of isopropanol to ethyl acetate is (0.5-1):1;

[0020] Step B: Next, dodecylamine is added to the first mixed solution in step A, and the reaction is continued under the above temperature conditions for another period of time, which is 18 to 30 hours, for example, 24 hours, to obtain a second mixed solution; in this step B, the mass ratio of dodecylamine to polyetheramine is (0.9 to 4.5):100;

[0021] Step C: Add a second mixed solvent to the second mixed solution from step B to achieve a certain solid content. Stir until homogeneous to obtain a modified fatty amine curing agent soluble in acrylate adhesives. After bottling, seal and refrigerate to extend the shelf life of the modified fatty amine curing agent. In step C, the solid content is 25%–50%, for example, 40%. The second mixed solvent is mainly a co-solvent, serving a dissolving function to provide a reaction environment for the copolymerization of polyetheramine, bismaleimide, and dodecylamine. To prevent the second mixed solution from gelling, the second mixed solvent must also contain isopropanol. For example, the second mixed solvent may contain isopropanol and ethyl acetate. In the later stages of the reaction, using isopropanol as a co-solvent is very beneficial for dissolving amines and prevents the second mixed solution from gelling. In this second mixed solution, the mass ratio of isopropanol to ethyl acetate is (0.5–1):1.

[0022] The present invention also provides a modified fatty amine curing agent soluble in acrylate adhesives obtained by the above preparation method. Specifically, the modified fatty amine curing agent soluble in acrylate adhesives of the present invention comprises polyetheramine, bismaleimide, dodecylamine, and isopropanol. The mass ratio of the polyetheramine, bismaleimide, and dodecylamine is 100:(16-83):(0.9-4.5).

[0023] The modified fatty amine curing agent of the present invention, which is soluble in acrylate adhesives, is also an epoxy resin curing agent. This modified fatty amine curing agent, which is soluble in acrylate adhesives, is end-capped with amine groups.

[0024] Example

[0025] A method for preparing a modified fatty amine curing agent soluble in acrylate adhesives, comprising the following steps:

[0026] Step A: Take 50 grams of ZD1200 polyetheramine and 8.87 grams of bismaleimide and add them to a four-necked flask equipped with a reflux condenser, a constant pressure dropping funnel, a stirrer, and a thermometer. The four-necked flask has a capacity of 0.5 liters. Add 58.87 grams of the first mixed solvent, which is a mixture of isopropanol and ethyl acetate, wherein isopropanol accounts for 34% of the total mass of the first mixed solvent and ethyl acetate accounts for 66% of the total mass of the first mixed solvent. Stir the mixture in a water bath at 60°C for 24 hours until the mixed solution turns reddish-brown to obtain the first mixed solution. A mechanical stirrer is used.

[0027] Step B: Next, add 0.46 g of dodecylamine to the first mixed solution from step A, and continue the reaction under stirring in a water bath at 60°C for 24 hours to obtain the second mixed solution;

[0028] Step C: Add 30.12 grams of a second mixed solvent to the second mixed solution in step B. This second mixed solvent is also a mixture of isopropanol and ethyl acetate, wherein isopropanol accounts for 34% of the total mass of the second mixed solvent and ethyl acetate accounts for 66% of the total mass of the second mixed solvent, so that its solid content reaches 40%. Stir evenly to obtain a modified fatty amine curing agent that can be dissolved in acrylic ester glue. After bottling, seal and refrigerate.

[0029] Experimental results:

[0030] Prepare 20 grams each of acrylate adhesives with introduced epoxy functional groups (acrylate adhesives are epoxy-modified), 2 grams, 2.4 grams, 2.8 grams, and 3 grams of modified fatty amine curing agents soluble in acrylate adhesives prepared in Example 1, and 0.05 grams of DMP-30. DMP-30 is a catalyst for epoxy resin curing, namely 2,4,6-tris(dimethylaminomethyl)phenol. Prepare new adhesives accordingly. Figure 1 As shown, from this Figure 1 It can be seen that: the prepared new adhesive is "clear" in appearance, indicating that the new adhesive can dissolve in acrylic adhesive; the high temperature resistance (210℃ for 4 hours) is "very good", indicating that the new adhesive has strong high temperature resistance; and there is no residue. Therefore, the modified fatty amine curing agent prepared in Example 1 that can dissolve in acrylic adhesive has good high temperature resistance, low polarity and flexibility, and can dissolve in acrylic adhesive.

[0031] Example

[0032] A method for preparing a modified fatty amine curing agent soluble in acrylate adhesives, comprising the following steps:

[0033] Step A: Take 30 grams of ZD140 polyetheramine and 24.75 grams of bismaleimide and add them to a four-necked flask equipped with a reflux condenser, a constant pressure dropping funnel, a stirrer, and a thermometer. The capacity of the four-necked flask is 0.5 liters. Add 55 grams of the first mixed solvent, which is a mixture of isopropanol and ethyl acetate, wherein isopropanol accounts for 50% of the total mass of the first mixed solvent and ethyl acetate accounts for 50% of the total mass of the first mixed solvent. Stir the mixture in a water bath at 85°C for 24 hours until the mixed solution turns reddish-brown to obtain the first mixed solution. A mechanical stirrer is used.

[0034] Step B: Next, add 1.28 g of dodecylamine to the first mixed solution from step A, and continue the reaction under stirring in a water bath at 85°C for 24 hours to obtain the second mixed solution;

[0035] Step C: Add 29.045 grams of a second mixed solvent to the second mixed solution in step B. The second mixed solvent is a mixture of isopropanol and ethyl acetate, wherein isopropanol accounts for 50% of the total mass of the second mixed solvent and ethyl acetate accounts for 50% of the total mass of the second mixed solvent, so that the solid content reaches 40%. Stir evenly to obtain a modified fatty amine curing agent that can be dissolved in acrylic ester glue. After bottling, seal and refrigerate.

[0036] Experimental results:

[0037] Prepare 20 grams each of acrylate adhesives with introduced epoxy functional groups, 2 grams, 2.4 grams, 2.8 grams, and 3 grams of modified fatty amine curing agents soluble in acrylate adhesives prepared in Example 2, and 0.05 grams of DMP-30. Prepare new adhesives accordingly. Figure 2 As shown, from this Figure 2 It can be seen that: the prepared new adhesive is "clear" in appearance, indicating that the new adhesive can dissolve in acrylic adhesive; the high temperature resistance (210℃ for 4 hours) is "very good", indicating that the new adhesive has strong high temperature resistance; and there is no residue. Therefore, the modified fatty amine curing agent prepared in Example 1 that can dissolve in acrylic adhesive has good high temperature resistance, low polarity and flexibility, and can dissolve in acrylic adhesive.

[0038] Example

[0039] A method for preparing a modified fatty amine curing agent soluble in acrylate adhesives, comprising the following steps:

[0040] Step A: Take 40 grams of ZD140 polyetheramine and 25 grams of bismaleimide and add them to a four-necked flask equipped with a reflux condenser, a constant pressure dropping funnel, a stirrer and a thermometer. The capacity of the four-necked flask is 0.5 liters. Then add 65 grams of the first mixed solvent, which is a mixture of isopropanol and ethyl acetate, wherein isopropanol accounts for 50% of the total mass of the first mixed solvent and ethyl acetate accounts for 50% of the total mass of the first mixed solvent. Stir the mixture in a water bath at 85°C for 24 hours until the mixed solution turns wine red to obtain the first mixed solution. A mechanical stirrer is used.

[0041] Step B: Next, add 0.71 g of dodecylamine to the first mixed solution from step A, and continue stirring the reaction in a water bath at 85°C for 24 hours to obtain the second mixed solution.

[0042] Step C: Add 33.565 grams of a second mixed solvent to the second mixed solution in step B. The second mixed solvent is a mixture of isopropanol and ethyl acetate, wherein isopropanol accounts for 50% of the total mass of the second mixed solvent and ethyl acetate accounts for 50% of the total mass of the second mixed solvent, so that the solid content reaches 40%. Stir evenly to obtain a modified fatty amine curing agent that can be dissolved in acrylic ester glue. After bottling, seal and refrigerate.

[0043] Experimental results:

[0044] Prepare 20 grams each of acrylate adhesives with introduced epoxy functional groups, 2 grams, 2.4 grams, 2.8 grams, and 3 grams of modified fatty amine curing agents soluble in acrylate adhesives prepared in Example 2, and 0.05 grams of DMP-30. Prepare new adhesives accordingly. Figure 3 As shown, from this Figure 3 It can be seen that: the prepared new adhesive is "clear" in appearance, indicating that the new adhesive can dissolve in acrylic adhesive; the high temperature resistance (210℃ for 4 hours) is "very good", indicating that the new adhesive has strong high temperature resistance; and there is no residue. Therefore, the modified fatty amine curing agent prepared in Example 1 that can dissolve in acrylic adhesive has good high temperature resistance, low polarity and flexibility, and can dissolve in acrylic adhesive.

[0045] The above-described embodiments are merely preferred embodiments of the present invention, and are described in a relatively specific and detailed manner. However, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements are all within the scope of protection of the present invention. Therefore, all equivalent transformations and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.

Claims

1. A method for preparing a modified fatty amine curing agent soluble in acrylate adhesives, characterized in that, Includes the following steps: Step A: Add polyetheramine and bismaleimide to a flask, add a certain amount of the first mixed solvent, and stir in a water bath at a certain temperature for a period of time to obtain the first mixed solution. The mass ratio of polyetheramine to bismaleimide is 100:(16-83); the temperature in the water bath is 50-100℃. Step B: Next, dodecylamine is added to the first mixed solution in step A, and the reaction is continued under the temperature conditions of step A for another period of time to obtain a second mixed solution. The mass ratio of dodecylamine to polyetheramine is (0.9~4.5):

100. Step C: Add the second mixed solvent to the second mixed solution in step B to make its solid content reach a certain value, stir evenly, and you will get a modified fatty amine curing agent that can be dissolved in acrylic ester glue. After bottling, seal and refrigerate.

2. The method for preparing the modified fatty amine curing agent soluble in acrylate adhesives according to claim 1, characterized in that: In steps A and C, both the first mixed solvent and the second mixed solvent contain isopropanol.

3. The method for preparing the modified fatty amine curing agent soluble in acrylate adhesives according to claim 2, characterized in that: In steps A and C, both the first mixed solvent and the second mixed solvent further contain ethyl acetate.

4. The method for preparing the modified fatty amine curing agent soluble in acrylate adhesives according to claim 3, characterized in that: The mass ratio of isopropanol to ethyl acetate is (0.5-1):

1.

5. The method for preparing the modified fatty amine curing agent soluble in acrylate adhesives according to claim 1, characterized in that: In step C, the solid content is 25% to 50%.

6. A modified aliphatic amine curing agent soluble in acrylate adhesives, characterized in that: Modified fatty amine curing agent soluble in acrylate adhesives, prepared by any one of claims 1 to 5.

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