Low-dielectric epoxy resin curing agent and preparation method thereof

Abstract

The invention discloses a low-dielectric epoxy resin curing agent and a preparation method thereof, and belongs to the technical field of curing agent preparation, the low-dielectric epoxy resin curing agent comprises the following components: aliphatic amine, alicyclic amine, hexahydrophthalic anhydride, a low-dielectric additive and a diluent; according to the method, a homogenization treatment process aiming at a nano material in the low-dielectric additive is arranged in the method, so that the dispersion uniformity of particles of a mixed material can be effectively ensured, agglomeration is avoided, and the subsequent mixing effect of the material can be effectively ensured; according to the present invention, the reduced pressure distillation treatment can be performed on the mixture, such that the purity of the mixture can be substantially improved so as to ensure that the product meets the established quality standard and the performance requirement, and the production of the product with characteristics of excellent appearance, excellent function and excellent service life can be easily achieved; and the final quality of finished products is guaranteed, and defective products can be removed easily.

Description

Technical Field

[0001] The present invention belongs to the technical field of curing agent preparation, and particularly relates to a low-dielectric epoxy resin curing agent and a preparation method thereof. Background Art

[0002] A curing agent, also known as a hardener or crosslinking agent, is a type of chemical substance that can react chemically with resins (such as epoxy resins, polyurethanes, unsaturated polyesters, etc.) to transform them from a liquid or plastic state into a solid three-dimensional network structure. Curing agents are crucial in fields such as composite materials, adhesives, coatings, and electronic packaging. The selection and dosage of curing agents directly affect the performance of the final materials.

[0003] Chinese Patent Publication (CN105542128A) discloses an epoxy resin curing agent, a preparation method thereof, and uses thereof. The epoxy resin curing agent has a molecular structure shown in Formula I. By using an epoxy resin curing agent with a specific structure, the resin composition composed of it has good low-dielectric properties. Its cured product has a low dielectric constant and dielectric loss, and has good heat resistance. It is a low-dielectric material with relatively large economic efficiency and environmental friendliness. Although the current preparation methods can also achieve the preparation of curing agents, there are few pretreatment processes for materials, resulting in the inability to improve the mixing effect of materials during subsequent production processes. Moreover, there is no effective purification and curing treatment for the mixed materials later, so the overall performance and purity of the materials cannot be improved, and the application effect of the actual method is not good. To solve this problem, there is an urgent need for a low-dielectric epoxy resin curing agent and a preparation method thereof. Summary of the Invention

[0004] The purpose of the present invention is to propose a low-dielectric epoxy resin curing agent and a preparation method thereof to solve the problem that although the current preparation methods can also achieve the preparation of curing agents, there are few pretreatment processes for materials, resulting in the inability to improve the mixing effect of materials during subsequent production processes. Moreover, there is no effective purification and curing treatment for the mixed materials later, so the overall performance and purity of the materials cannot be improved, and the application effect of the actual method is not good.

[0005] To achieve the above purpose, the present invention adopts the following technical scheme: A low-dielectric epoxy resin curing agent, comprising the following components: aliphatic amine, cycloaliphatic amine, hexahydrophthalic anhydride, low-dielectric additive, and diluent.

[0006] As a further description of the above technical scheme:

[0007] The weight parts of the fatty amine, alicyclic amine, hexahydrophthalic anhydride, low-dielectric additive and reactive diluent are: 8-10 parts, 6-8 parts, 3-5 parts, 3-6 parts and 2-5 parts, wherein the low-dielectric additive is fluorinated epoxy resin, polysiloxane, hollow glass microspheres, silicon dioxide nanoparticles and boron nitride nanosheets, and the diluent is propylene oxide phenyl ether.

[0008] This article also discloses a preparation method of a low-dielectric epoxy resin curing agent, which includes the following steps:

[0009] S1. Take the hollow glass microspheres, silicon dioxide nanoparticles and boron nitride nanosheets in the low-dielectric additive, place them in a homogenizer, and process for a period of time.

[0010] S2. Take the fatty amine, alicyclic amine, hexahydrophthalic anhydride and low-dielectric additive and place them in a mixing device, and adjust the mixing rate to mix the raw materials.

[0011] S3. After a period of time, introduce a protective gas into the mixing device, control the temperature in the equipment, and continue to mix for a period of time.

[0012] S4. Add a catalyst to the mixture, raise the temperature to a certain level, and stir for a period of time.

[0013] S5. Carry out purification treatment on the mixture.

[0014] S6. Carry out aging treatment on the mixture.

[0015] S7. Carry out quality inspection and packaging storage of the finished product.

[0016] Furthermore, in this method, there is a homogenization process for the nanomaterials in the low-dielectric additive, which can effectively ensure the dispersion uniformity of the particles in the mixture, avoid agglomeration, and effectively ensure the subsequent mixing effect of the materials. At the same time, the method also has a purification process for the mixture, which can carry out vacuum distillation treatment on the mixture, greatly improving the purity of the mixture, thereby ensuring that it meets the established quality standards and performance requirements, and helping to produce products that are excellent in appearance, function and service life. In addition, the method also has an aging process for the mixture. Through aging, the microscopic structure inside the material may change, and these changes help to improve the overall performance of the material. Finally, multiple tests are carried out on the finished product to ensure the final quality of the finished product and help to eliminate defective products.

[0017] As a further description of the above technical solution:

[0018] In S1, take the hollow glass microspheres, silicon dioxide nanoparticles and boron nitride nanosheets in the low-dielectric additive, place them in a homogenizer, and process for 1-2 h.

[0019] As a further description of the above technical solution:

[0020] In S2, take fatty amine, alicyclic amine, hexahydrophthalic anhydride and low-dielectric additive and place them in a mixing device, adjust the mixing rate to 600 - 800 r / min to mix the raw materials.

[0021] As a further description of the above technical solution:

[0022] In S3, after 15 - 20 min, introduce a protective gas into the mixing device, control the temperature inside the equipment to 40 - 50 °C, and continue mixing for 35 - 45 min. The protective gas introduced is one of nitrogen and argon.

[0023] As a further description of the above technical solution:

[0024] In S4, add a catalyst to the mixture, raise the temperature to 55 - 60 °C, and stir for 25 - 35 min.

[0025] As a further description of the above technical solution:

[0026] In S5, perform purification treatment on the mixture. The specific steps are as follows: First, perform vacuum distillation on the mixture, place it in a vacuum environment, raise the temperature to 80 - 90 °C, remove the solvent until the residual amount < 1%, and finally introduce the mixture onto a microporous filter membrane for filtration. The pore size of the microporous filter membrane is 0.5 - 1.5 μm.

[0027] As a further description of the above technical solution:

[0028] In S6, perform curing treatment on the mixture. The specific steps are as follows: Let the mixture stand at room temperature for 24 - 48 h to eliminate internal stress and stabilize the system, and add a reactive diluent to adjust the viscosity of the curing agent to the applicable range. The applicable range of the viscosity of the curing agent is 200 - 500 mPa·s.

[0029] As a further description of the above technical solution:

[0030] In S7, perform quality inspection and packaging storage on the finished product. Specifically: Perform performance tests, including testing the dielectric constant, curing speed, and storage stability. The conditions for packaging storage are: Store in a sealed and light-proof manner, and the storage temperature is 10 - 20 °C.

[0031] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0032] This method can effectively ensure the dispersion uniformity of the particles in the mixture and avoid agglomeration by setting a homogenization process for the nanomaterials in the low-dielectric additive inside. It can effectively guarantee the subsequent mixing effect of the materials. At the same time, a purification process for the mixture is also set in the method, which can perform vacuum distillation on the mixture and greatly improve the purity of the mixture, thereby ensuring that it meets the established quality standards and performance requirements, and contributing to the production of products that are excellent in appearance, function, and service life. In addition, a ripening process for the mixture is also set in the method. Through ripening, the microscopic structure inside the material may change, and these changes help to improve the overall performance of the material. Finally, multiple tests are also carried out on the finished product to ensure the final quality of the finished product and help to eliminate defective products. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a flowchart of a preparation method for a low-dielectric epoxy resin curing agent. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0034] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0035] Embodiment 1

[0036] Please refer to Figure 1 , the present invention provides a technical solution: a low-dielectric epoxy resin curing agent, including the following components: aliphatic amine, cycloaliphatic amine, hexahydrophthalic anhydride, low-dielectric additive, and diluent, with the weight parts being: 8 parts, 6 parts, 3 parts, 3 parts, and 2 parts. Among them, the low-dielectric additive is fluorinated epoxy resin, polysiloxane, hollow glass microspheres, silicon dioxide nanoparticles, and boron nitride nanosheets, and the diluent is propylene oxide phenyl ether.

[0037] This article also discloses a preparation method for a low-dielectric epoxy resin curing agent, including the following steps:

[0038] S1. Take the hollow glass microspheres, silicon dioxide nanoparticles, and boron nitride nanosheets in the low-dielectric additive, place them in a homogenizer, and process for 1 h;

[0039] S2. Take the aliphatic amine, cycloaliphatic amine, hexahydrophthalic anhydride, and low-dielectric additive and place them in a mixing device, and adjust the mixing rate to 600 r / min to mix the raw materials;

[0040] S3. After 15 minutes, introduce a protective gas into the mixing device, control the temperature inside the equipment to 40 °C, and continue mixing for 35 minutes. The protective gas introduced is nitrogen;

[0041] S4. Add a catalyst to the mixed materials, raise the temperature to 55 °C, and stir for 25 minutes;

[0042] S5. Conduct purification treatment on the mixed materials. The specific steps are as follows: First, perform vacuum distillation on the mixed materials. Place them in a vacuum environment, raise the temperature to 80 °C, remove the solvent until the residual amount is <1%, and finally introduce the mixed materials onto a microporous filter membrane for filtration. The pore size of the microporous filter membrane is 0.5 μm;

[0043] S6. Conduct curing treatment on the mixed materials. The specific steps are as follows: Let the mixed materials stand at room temperature for 24 - 48 hours to eliminate internal stress and stabilize the system. Add a reactive diluent to adjust the viscosity of the curing agent to the applicable range. The applicable range of the curing agent viscosity is 200 - 500 mPa·s;

[0044] S7. Conduct quality inspection and packaging storage of the finished product. Specifically: Conduct performance tests, including testing the dielectric constant, curing speed, and storage stability. The conditions for packaging storage are: Store in a sealed and light - proof manner, and the storage temperature is 10 °C.

[0045] In this embodiment, this method can effectively ensure the dispersion uniformity of the particles in the mixed materials and avoid agglomeration through a homogenization process for the nano - materials in the low - dielectric additive inside, and can effectively ensure the subsequent mixing effect of the materials.

[0046] Example 2

[0047] Please refer to Figure 1 , the present invention provides a technical solution: A low - dielectric epoxy resin curing agent, comprising the following components: aliphatic amine, cycloaliphatic amine, hexahydrophthalic anhydride, low - dielectric additive, and diluent, with the weight fractions being: 9 parts, 7 parts, 4 parts, 5 parts, and 3 parts. Among them, the low - dielectric additive is fluorinated epoxy resin, polysiloxane, hollow glass microspheres, silicon dioxide nanoparticles, and boron nitride nanosheets, and the diluent is propylene oxide phenyl ether.

[0048] This article also discloses a preparation method for a low - dielectric epoxy resin curing agent, comprising the following steps:

[0049] S1. Take the hollow glass microspheres, silicon dioxide nanoparticles, and boron nitride nanosheets in the low - dielectric additive, place them in a homogenizer, and process for 1.5 hours;

[0050] S2. Take the aliphatic amine, cycloaliphatic amine, hexahydrophthalic anhydride, and low - dielectric additive and place them in a mixing device, adjust the mixing rate to 700 r / min, and mix the raw materials;

[0051] S3. After 15 minutes, introduce a protective gas into the mixing device, control the temperature inside the equipment to 45 °C, and continue mixing for 40 minutes. The protective gas introduced is argon;

[0052] S4. Add a catalyst to the mixed material, raise the temperature to 58 °C, and stir for 28 minutes;

[0053] S5. Conduct purification treatment on the mixed material. The specific steps are as follows: First, perform vacuum distillation on the mixed material, place it in a vacuum environment, raise the temperature to 85 °C, remove the solvent until the residual amount is <1%, and finally introduce the mixed material onto a microporous filter membrane for filtration. The pore size of the microporous filter membrane is 1.0 μm;

[0054] S6. Conduct aging treatment on the mixed material. The specific steps are as follows: Let the mixed material stand at room temperature for 24 - 48 hours to eliminate internal stress and stabilize the system, and add a reactive diluent to adjust the viscosity of the curing agent to the applicable range. The applicable range of the curing agent viscosity is 200 - 500 mPa·s;

[0055] S7. Conduct quality inspection and packaging storage of the finished product. Specifically: Conduct performance tests, including testing the dielectric constant, curing speed, and storage stability. The conditions for packaging storage are: Store in a sealed and light - proof manner, and the storage temperature is 15 °C.

[0056] In this embodiment, a purification treatment process for the mixed material is provided, which can perform vacuum distillation on the mixed material, greatly improve the purity of the mixed material, thereby ensuring that it meets the established quality standards and performance requirements, and helping to produce products that are excellent in appearance, function, and service life.

[0057] Example 3

[0058] Please refer to Figure 1 , the present invention provides a technical solution: A low - dielectric epoxy resin curing agent, comprising the following components: aliphatic amine, cycloaliphatic amine, hexahydrophthalic anhydride, low - dielectric additive, and diluent, with the weight parts being: 10 parts, 8 parts, 5 parts, 6 parts, and 5 parts. Among them, the low - dielectric additive is fluorinated epoxy resin, polysiloxane, hollow glass microspheres, silicon dioxide nanoparticles, and boron nitride nanosheets, and the diluent is propylene oxide phenyl ether.

[0059] This article also discloses a preparation method of a low - dielectric epoxy resin curing agent, comprising the following steps:

[0060] S1. Take the hollow glass microspheres, silicon dioxide nanoparticles, and boron nitride nanosheets in the low - dielectric additive, place them in a homogenizer, and process for 2 hours;

[0061] S2. Take fatty amine, alicyclic amine, hexahydrophthalic anhydride and low-dielectric additive and place them in a mixing device. Adjust the mixing rate to 800 r / min to mix the raw materials.

[0062] S3. After 18 min, introduce a protective gas into the mixing device, control the temperature inside the equipment to 50 °C, and continue mixing for 45 min. The protective gas introduced is nitrogen.

[0063] S4. Add a catalyst to the mixture, raise the temperature to 60 °C, and stir for 35 min.

[0064] S5. Carry out purification treatment on the mixture. The specific steps are as follows: First, carry out vacuum distillation treatment on the mixture, place it in a vacuum environment, raise the temperature to 90 °C, remove the solvent until the residual amount < 1%, and finally introduce the mixture onto a microporous filter membrane for filtration treatment. The pore size of the microporous filter membrane is 1.5 μm.

[0065] S6. Carry out curing treatment on the mixture. The specific steps are as follows: Let the mixture stand at room temperature for 48 h to eliminate internal stress and stabilize the system, add a reactive diluent to adjust the viscosity of the curing agent to the applicable range. The applicable range of the viscosity of the curing agent is 200 - 500 mPa·s.

[0066] S7. Carry out quality inspection and packaging storage of the finished product. Specifically: Carry out performance tests, including testing the dielectric constant, curing speed and storage stability. The conditions for packaging storage are: Store in a sealed and light-proof manner, and the storage temperature is 20 °C.

[0067] In this embodiment, this method is provided with a curing treatment process for the mixture. Through curing, the microscopic structure inside the material may change, and these changes help to improve the overall performance of the material. Finally, multiple tests are also carried out on the finished product to ensure the final quality of the finished product and help to eliminate defective products.

[0068] Example 4

[0069] Please refer to Figure 1 , the present invention provides a technical solution: A low-dielectric epoxy resin curing agent, including the following components: fatty amine, alicyclic amine, hexahydrophthalic anhydride, low-dielectric additive and diluent, with the weight parts being: 10 parts, 8 parts, 5 parts, 6 parts and 5 parts. Among them, the low-dielectric additive is fluorinated epoxy resin, polysiloxane, hollow glass microspheres, silicon dioxide nanoparticles and boron nitride nanosheets, and the diluent is propylene oxide phenyl ether.

[0070] This article also discloses a preparation method for a low-dielectric epoxy resin curing agent, including the following steps:

[0071] S1. Take the hollow glass microspheres, silicon dioxide nanoparticles and boron nitride nanosheets in the low-dielectric additive, place them in a homogenizer, and process for 2 h.

[0072] S2. Place fatty amine, cycloaliphatic amine, hexahydrophthalic anhydride and low-dielectric additive into a mixing device, and adjust the mixing rate to 750 r / min to mix the raw materials;

[0073] S3. After 20 min, introduce a protective gas into the mixing device, control the temperature inside the equipment to 50 °C, and continue mixing for 45 min. The protective gas introduced is nitrogen;

[0074] S4. Add a catalyst to the mixture, raise the temperature to 60 °C, and stir for 35 min;

[0075] S5. Conduct purification treatment on the mixture. The specific steps are as follows: First, conduct vacuum distillation treatment on the mixture, place it in a vacuum environment, raise the temperature to 85 °C, remove the solvent until the residual amount < 1%, and finally introduce the mixture onto a microporous filter membrane for filtration. The pore size of the microporous filter membrane is 1.3 μm;

[0076] S6. Conduct aging treatment on the mixture. The specific steps are as follows: Let the mixture stand at room temperature for 42 h to eliminate internal stress and stabilize the system, and add a reactive diluent to adjust the viscosity of the curing agent to the applicable range. The applicable range of the curing agent viscosity is 200 - 500 mPa·s;

[0077] S7. Conduct quality inspection, packaging and storage of the finished product. Specifically: Conduct performance tests, including testing the dielectric constant, curing speed and storage stability. The conditions for packaging and storage are: Store in a sealed and light-proof manner, and the storage temperature is 20 °C.

[0078] In this embodiment, this method can effectively ensure the dispersion uniformity of the particles in the mixture and avoid agglomeration by setting a homogenization process for the nanomaterials in the low-dielectric additive inside, which can effectively ensure the subsequent mixing effect of the materials. At the same time, the method also has a purification process for the mixture, which can conduct vacuum distillation treatment on the mixture, greatly improving the purity of the mixture, thus ensuring that it meets the established quality standards and performance requirements, helping to produce products that are excellent in appearance, function and service life. And the method also has an aging process for the mixture. Through aging, the microscopic structure inside the material may change, and these changes help to improve the overall performance of the material. Finally, multiple tests are also conducted on the finished product to ensure the final quality of the finished product and help to eliminate defective products.

[0079] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution of the present invention and its inventive concept, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

Claims

1. A low dielectric epoxy resin curing agent, characterized in that: The invention comprises the following ingredients: aliphatic amine, alicyclic amine, hexahydrophthalic anhydride, a low dielectric additive and a diluent.

2. A low dielectric epoxy resin curing agent according to claim 1, characterized in that: The weight proportions of the fatty amine, alicyclic amine, hexahydrophthalic anhydride, low dielectric additive and reactive diluent are: 8-10 parts, 6-8 parts, 3-5 parts, 3-6 parts and 2-5 parts, wherein the low dielectric additive is fluoroepoxy resin, polysiloxane, hollow glass microspheres, silicon dioxide nanoparticles and boron nitride nanosheets, and the diluent is propylene oxide phenyl ether.

3. A method for preparing a low dielectric epoxy resin curing agent, characterized in that: The steps include: S1, taking the hollow glass microspheres, silicon dioxide nanoparticles and boron nitride nanosheets in the low dielectric additive, placing them in a homogenizer and treating them for a period of time; S2, placing aliphatic amine, alicyclic amine, hexahydrophthalic anhydride and low dielectric additive in a mixing device, and adjusting the mixing rate to mix the raw materials; S3. After a period of time, introduce protective gas into the mixing device, control the temperature inside the equipment, and continue mixing for a period of time; S4, adding a catalyst to the mixture, raising the temperature to a certain level, and stirring for a period of time; S5, performing mixed material purification treatment; S6, performing a aging treatment on the mixed material; S7. Conduct quality inspection, packaging and storage of finished products.

4. The method for preparing a low dielectric epoxy resin curing agent according to claim 3, characterized in that: In S1, the hollow glass microspheres, silicon dioxide nanoparticles and boron nitride nanosheets in the low dielectric additive are placed in a homogenizer and processed for 1-2 hours.

5. The method for preparing a low dielectric epoxy resin curing agent according to claim 3, characterized in that: In S2, aliphatic amine, alicyclic amine, hexahydrophthalic anhydride and low dielectric additive are placed in a mixing device, and the mixing rate is adjusted to 600-800 r / min to mix the raw materials.

6. The method for preparing a low dielectric epoxy resin curing agent according to claim 3, characterized in that: In S3, after 15-20 minutes, a protective gas is introduced into the mixing device, the temperature in the device is controlled to 40-50° C., and mixing is continued for 35-45 minutes. The protective gas introduced is one of nitrogen and argon.

7. The method for preparing a low dielectric epoxy resin curing agent according to claim 3, characterized in that: In S4, a catalyst is added to the mixture, the temperature is raised to 55-60° C., and the mixture is stirred for 25-35 minutes.

8. The method for preparing a low dielectric epoxy resin curing agent according to claim 3, characterized in that: In S5, the mixture is purified, and the specific steps are as follows: first, the mixture is subjected to reduced pressure distillation, placed in a vacuum environment, heated to 80-90°C, and the solvent is removed until the residual amount is less than 1%, and finally the mixture is introduced into a microporous filter membrane for filtration, and the pore size of the microporous filter membrane is 0.5-1.5μm.

9. The method for preparing a low dielectric epoxy resin curing agent according to claim 3, characterized in that: In S6, the mixture is aged, and the specific steps are: the mixture is allowed to stand at room temperature for 24-48 hours to eliminate internal stress and stabilize the system, and a reactive diluent is added to adjust the viscosity of the curing agent to an applicable range. The applicable range of the curing agent viscosity is 200-500 mPa·s.

10. The method for preparing a low dielectric epoxy resin curing agent according to claim 3, characterized in that: In S7, the finished product is subjected to quality inspection and packaging and storage, specifically, performance testing is performed, including testing of dielectric constant, curing speed and storage stability. The packaging and storage conditions are as follows: sealed and light-proof storage at a storage temperature of 10-20°C.

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