Transparent multifunctional epoxy resin composite material and preparation method thereof

Abstract

The invention discloses a transparent multifunctional epoxy resin composite material and a preparation method thereof, and relates to the technical field of high-molecular compound materials. The low-dielectric-constant polymer is prepared by polymerizing 1-(3-allyl-2, 4-dihydroxyphenyl) ethanone, 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4, 4 '-dichlorodiphenyl sulfone, and the components in the epoxy resin composite material are optimally designed, so that the dielectric loss of epoxy resin can be effectively reduced, and the dielectric constant of the epoxy resin composite material is improved. Zinc oxide and aluminum silicate nano powder are additionally added, and the materials have lower dielectric constant and dielectric loss, so that the dielectric property of the epoxy resin composite material is optimized. The low-dielectric-constant polymer is combined with the epoxy resin, the silane coupling agent, the aluminum silicate nano powder and the zinc oxide through chemical bonds, so that the epoxy resin composite material is endowed with excellent moisture resistance, the reliability of the epoxy resin composite material in a severe environment is improved, and the service life of the epoxy resin composite material is prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of polymer compound materials, in particular to a transparent multifunctional epoxy resin composite material and a preparation method thereof. Background Art

[0002] In today's society, with the rapid development of informatization, the speed of information processing and information dissemination is becoming faster and faster. In order to adapt to this trend, electronic products are constantly developing in the direction of being thinner, shorter and more multifunctional. This trend has led to a significant increase in the density of components inside electronic products, followed by delays in signal transmission, increased crosstalk noise and increased energy consumption. Among these problems, signal delay is particularly prominent, so there is an urgent need for a composite material with low dielectric constant and low dielectric loss as a substrate material for electronic products. In electronic circuits, the propagation speed of the signal is directly related to the dielectric constant of the base material. The lower the dielectric constant, the faster the signal propagation speed.

[0003] In today's industry, epoxy resin, polyimide resin and polytetrafluoroethylene are three common types of resins used as printed circuit board substrate materials. Polytetrafluoroethylene has attracted much attention due to its excellent dielectric properties, but it also has some defects that cannot be ignored: its processability is poor, its mechanical properties and bonding properties are not ideal, and its cost is relatively high. Although polyimide resin performs well in some aspects, its processing and molding are difficult, and its comprehensive performance is not satisfactory. In contrast, epoxy resin is favored because of its wide source of raw materials, low price and easy processing and molding. After curing, epoxy resin exhibits excellent physical and chemical properties, including good solvent resistance, low linear expansion rate, high mechanical strength, excellent thermal stability and dielectric properties, and tolerance to surface leakage and arcing, which makes it the first choice for composite materials widely used in printed circuit boards. However, with the rapid development of microelectronics technology, the dielectric properties of pure epoxy resin can no longer meet the strict requirements of modern low-dielectric materials. Therefore, how to further reduce the dielectric constant of epoxy resin matrix materials has become a key issue that needs to be urgently addressed in current research and industry. Summary of the invention

[0004] The object of the present invention is to provide a transparent multifunctional epoxy resin composite material and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, on the one hand, the present invention provides a transparent multifunctional epoxy resin composite material, which is composed of the following components:

[0006]

[0007] Further, the epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin, and its epoxy equivalent is 180 - 250 g / eq.

[0008] Further, the solvent is xylene.

[0009] Further, the dispersant is polyoxyethylene alkyl ether or sodium dodecylbenzenesulfonate.

[0010] Further, the silane coupling agent is a double bond-containing coupling agent.

[0011] Further, the preparation method of the low dielectric polymer is as follows: Pour 75 mL of N-methylpyrrolidone and 25 mL of toluene into a three-necked flask, and sequentially add 0.07 - 0.1 mol of 1-(3-allyl-2,4-dihydroxyphenyl)ethanone, 0.01 - 0.04 mol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.08 - 0.2 mol of 4,4'-dichlorodiphenyl sulfone, and 0.1 - 0.2 mol of anhydrous potassium carbonate. Then add a certain amount of toluene to the water separator to make the liquid level flush with the neck of the water separator. Turn on the electric heating mantle and slowly heat up to 140 °C. After dehydrating for 3 h, drain the water and toluene in the water separator together, and keep the water separator switch open. When the system temperature reaches 190 °C, continue the reaction for 5 h. After polymerization, pour it into a large amount of water for precipitation, then crush it and acidify it with dilute hydrochloric acid to remove the excessive anhydrous potassium carbonate, unreacted small molecules and oligomers. Filter to obtain the solid, and dry it in vacuum at 100 °C for 12 h.

[0012] Further, the curing agent is MHHPA.

[0013] On the other hand, the present invention provides a preparation method of a transparent multifunctional epoxy resin composite material, including the following preparation steps: Mix the silane coupling agent, solvent, aluminum silicate nanoflour, and zinc oxide, stir at 60 °C and 80 rpm for 30 min, then add the low dielectric polymer, epoxy resin, and dispersant, continue to stir evenly, add the curing agent and AIBN, and carry out curing treatment.

[0014] Further, the curing treatment is as follows: Pour it into a mold preheated at 80 °C, cure at 80 °C for 1 h, then raise the temperature to 130 - 140 °C and cure for 4 h, and then raise the temperature to 150 - 200 °C and cure for 2 h.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0016] (1) The present invention polymerizes 1-(3-allyl-2,4-dihydroxyphenyl)ethanone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 4,4'-dichlorodiphenyl sulfone to obtain a low dielectric constant polymer. Since two trifluoromethyl groups are relatively close to each other and have a very strong electron-withdrawing ability, the charge transfer in the structural unit and the formation of charge transfer complexes in the molecule are significantly reduced, effectively lowering the dielectric constant of the polymer. The components in the epoxy resin composite are optimized, which can effectively reduce the dielectric loss of the epoxy resin. In addition, zinc oxide and aluminum silicate nanoflour are additionally added in the present invention. The above materials have low dielectric constant and dielectric loss, optimizing the dielectric properties of the epoxy resin composite.

[0017] (2) The present invention chemically reacts the low dielectric constant polymer with epoxy resin and silane coupling agent to form strong chemical bonds, significantly enhancing the mechanical strength of the epoxy resin composite, forming a dense interfacial layer, reducing bubbles and defects, and improving the reliability of the epoxy resin composite. In addition, the silane coupling agent, aluminum silicate nanoflour, and zinc oxide are further chemically bonded, endowing the epoxy resin composite with excellent moisture resistance, improving the reliability of the epoxy resin composite in harsh environments, and extending the service life of the epoxy resin composite.

[0018] (3) The dispersant and the solvent cooperate to achieve uniform dispersion of the nano-fillers (aluminum silicate, zinc oxide), reduce light scattering, and enable the material to maintain a light transmittance of more than 80% in the visible light band, meeting the requirements of optical devices. Detailed Embodiments

[0019] 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 of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0020] Example 1

[0021] A transparent multifunctional epoxy resin composite, which is composed of the following components:

[0022]

[0023]

[0024] The preparation method of the low-dielectric polymer is as follows: Pour 75 mL of N-methylpyrrolidone and 25 mL of toluene into a three-necked flask, and sequentially add 0.07 mol of 1-(3-allyl-2,4-dihydroxyphenyl)ethanone, 0.01 mol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.08 mol of 4,4′-dichlorodiphenyl sulfone, and 0.1 mol of anhydrous potassium carbonate. Then add a certain amount of toluene to the water separator to make the liquid level flush with the neck of the water separator. Turn on the electric heating mantle and slowly heat up to 140 °C. After dehydrating for 3 h, discharge the water and toluene in the water separator together, and keep the switch of the water separator in the open state. When the system temperature reaches 190 °C, continue the reaction for 5 h. After polymerization is completed, pour it into a large amount of water for precipitation, then crush it and acidify it with dilute hydrochloric acid to remove the excessive anhydrous potassium carbonate, unreacted small molecules and oligomers. Filter to obtain the solid, and dry it in vacuum at 100 °C for 12 h;

[0025] The preparation steps of the transparent multifunctional epoxy resin composite material include: Mix a silane coupling agent, a solvent, aluminum silicate nanoflakes with a particle size of 50 nm, and zinc oxide with a particle size of 50 nm, stir at 60 °C and 80 rpm for 30 min, then add the low-dielectric polymer, epoxy resin, and dispersant, continue to stir evenly, add a curing agent to obtain a high-molecular compound material solution. Mix the high-molecular compound material solution and AIBN in a mass ratio of 100:5, pour it into a mold preheated at 80 °C, cure at 80 °C for 1 h, then raise the temperature to 130 °C and cure for 4 h, and then raise the temperature to 150 °C and cure for 2 h.

[0026] Example 2

[0027] A transparent multifunctional epoxy resin composite material, which is composed of the following components:

[0028]

[0029]

[0030] The preparation method of the low-dielectric polymer is as follows: Pour 75 mL of N-methylpyrrolidone and 25 mL of toluene into a three-necked flask, and successively add 0.075 mol of 1-(3-allyl-2,4-dihydroxyphenyl)ethanone, 0.02 mol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.09 mol of 4,4'-dichlorodiphenyl sulfone, and 0.12 mol of anhydrous potassium carbonate. Then add a certain amount of toluene to the water separator to make the liquid level flush with the neck of the water separator. Turn on the electric heating mantle and slowly heat up to 140 °C. After dehydration for 3 h, drain the water and toluene in the water separator together, and keep the water separator switch in the open state. When the system temperature reaches 190 °C, continue the reaction for 5 h. After polymerization is completed, pour it into a large amount of water for precipitation, then crush it and acidify it with dilute hydrochloric acid to remove the excessive anhydrous potassium carbonate, unreacted small molecules and oligomers. Filter to obtain the solid, and dry it in vacuum at 100 °C for 12 h;

[0031] The preparation of the epoxy resin composite material includes the following steps: Mix a silane coupling agent, a solvent, aluminum silicate nanoflakes with a particle size of 50 nm, and zinc oxide with a particle size of 50 nm, stir at 60 °C and 80 rpm for 30 min, then add the low-dielectric polymer, epoxy resin, and dispersant, continue to stir evenly, add a curing agent to obtain a high-molecular compound material solution. Mix the high-molecular compound material solution and AIBN according to a mass ratio of 100:5, pour it into a mold preheated at 80 °C, cure at 80 °C for 1 h, then raise the temperature to 135 °C and cure for 4 h, and then raise the temperature to 160 °C and cure for 2 h.

[0032] Example 3

[0033] A transparent and multifunctional epoxy resin composite material, which is composed of the following components:

[0034]

[0035] The preparation method of the low-dielectric polymer is as follows: Pour 75 mL of N-methylpyrrolidone and 25 mL of toluene into a three-necked flask, and sequentially add 0.09 mol of 1-(3-allyl-2,4-dihydroxyphenyl)ethanone, 0.03 mol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.1 mol of 4,4'-dichlorodiphenyl sulfone, and 0.1 - 0.2 mol of anhydrous potassium carbonate. Then add a certain amount of toluene to the water separator to make the liquid level flush with the neck of the water separator. Turn on the electric heating mantle and slowly heat up to 140 °C. After dehydrating for 3 h, drain the water and toluene in the water separator together, and keep the water separator switch in the open state. When the system temperature reaches 190 °C, continue the reaction for 5 h. After polymerization is completed, pour it into a large amount of water for precipitation, then crush it and acidify it with dilute hydrochloric acid to remove the excessive anhydrous potassium carbonate, unreacted small molecules and oligomers. Filter to obtain the solid, and dry it in vacuum at 100 °C for 12 h;

[0036] The preparation steps of the epoxy resin composite material include: Mix a silane coupling agent, a solvent, aluminum silicate nanoflakes with a particle size of 50 nm, and zinc oxide with a particle size of 50 nm, stir at 60 °C and 80 rpm for 30 min, then add the low-dielectric polymer, epoxy resin, and dispersant, continue to stir evenly, add a curing agent to obtain a high-molecular compound material solution. Mix the high-molecular compound material solution and AIBN according to a mass ratio of 100:5, pour it into a mold preheated at 80 °C, cure at 80 °C for 1 h, then raise the temperature to 140 °C and cure for 4 h, and then raise the temperature to 180 °C and cure for 2 h.

[0037] Example 4

[0038] A transparent multifunctional epoxy resin composite material, which is composed of the following components:

[0039]

[0040] The preparation method of the low-dielectric polymer is as follows: Pour 75 mL of N-methylpyrrolidone and 25 mL of toluene into a three-necked flask, and sequentially add 0.1 mol of 1-(3-allyl-2,4-dihydroxyphenyl)ethanone, 0.04 mol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.2 mol of 4,4'-dichlorodiphenyl sulfone, and 0.2 mol of anhydrous potassium carbonate. Then add a certain amount of toluene to the water separator to make the liquid level flush with the neck of the water separator. Turn on the electric heating mantle and slowly heat up to 140 °C. After dehydration for 3 h, drain the water and toluene in the water separator together, and keep the switch of the water separator open. When the system temperature reaches 190 °C, continue the reaction for 5 h. After polymerization is completed, pour it into a large amount of water for precipitation, then crush it and acidify it with dilute hydrochloric acid to remove excessive anhydrous potassium carbonate, unreacted small molecules and oligomers. Filter to obtain the solid, and dry it in vacuo at 100 °C for 12 h;

[0041] The preparation steps of the epoxy resin composite material are as follows: Mix a silane coupling agent, a solvent, aluminum silicate nanoflakes with a particle size of 50 nm, and zinc oxide with a particle size of 50 nm, stir at 60 °C and 80 rpm for 30 min, then add a low-dielectric polymer, an epoxy resin, and a dispersant, continue to stir evenly, add a curing agent to obtain a high-molecular compound material solution. Mix the high-molecular compound material solution and AIBN in a mass ratio of 100:5, pour it into a mold preheated at 80 °C, cure at 80 °C for 1 h, then raise the temperature to 140 °C and cure for 4 h, and then raise the temperature to 200 °C and cure for 2 h.

[0042] Comparative Example 1

[0043] The difference between Comparative Example 1 and Example 1 is that no low-dielectric polymer is added, and the remaining steps are the same as those in Example 1.

[0044] Comparative Example 2

[0045] The difference between Comparative Example 2 and Example 1 is that no allyldimethoxysilane is added, and the remaining steps are the same as those in Example 1.

[0046] Comparative Example 3

[0047] The difference between Comparative Example 3 and Example 1 is that no aluminum silicate nanoflakes are added, and the remaining steps are the same as those in Example 1.

[0048] Comparative Example 4

[0049] The difference between Comparative Example 4 and Example 1 is that no zinc oxide is added, and the remaining steps are the same as those in Example 1.

[0050] Effect Example

[0051] The performance analysis results of the epoxy resin composite materials of Examples 1 to 4 and Comparative Examples 1 to 4 of the present invention are given in Table 1 below.

[0052] Table 1

[0053]

[0054]

[0055] The present invention polymerizes 1-(3-allyl-2,4-dihydroxyphenyl)ethanone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 4,4'-dichlorodiphenyl sulfone to obtain a low dielectric constant polymer. Since the two trifluoromethyl groups are relatively close and have a very strong electron-withdrawing ability, it significantly reduces the charge transfer in the structural unit and the formation of charge transfer complexes in the molecule, effectively reducing the dielectric constant of the polymer. The components in the epoxy resin composite are optimized, which can effectively reduce the dielectric loss of the epoxy resin. In addition, zinc oxide and aluminum silicate nanofluids are additionally added in the present invention. The above materials have low dielectric constants and dielectric losses, optimizing the dielectric properties of the epoxy resin composite. The present invention chemically reacts the low dielectric constant polymer with epoxy resin and silane coupling agent to form strong chemical bonds, significantly enhancing the mechanical strength of the epoxy resin composite, forming a dense interfacial layer, reducing bubbles and defects, and improving the reliability of the epoxy resin composite. In addition, epoxy resin, silane coupling agent, aluminum silicate nanofluids, and zinc oxide are bonded by chemical bonds, endowing the epoxy resin composite with excellent moisture resistance, improving the reliability of the epoxy resin composite in harsh environments, and extending the service life of the epoxy resin composite.

[0056] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claimed claims.

Claims

1. A transparent multifunctional epoxy resin composite material, characterized in that, The epoxy resin composite material consists of the following components:

2. The transparent multifunctional epoxy resin composite material according to claim 1, wherein The epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin, and its epoxy equivalent is 180 - 250 g / eq.

3. A transparent multifunctional epoxy resin composite according to claim 1, characterized in that, The solvent is xylene.

4. A transparent multifunctional epoxy resin composite according to claim 1, characterized in that, The dispersant is polyoxyethylene alkyl ether or sodium dodecylbenzenesulfonate.

5. A transparent multifunctional epoxy resin composite according to claim 1, characterized in that, The silane coupling agent is a double-bond-containing coupling agent.

6. A transparent multifunctional epoxy resin composite according to claim 1, characterized in that, The preparation method of the low-dielectric polymer is as follows: Pour 75 mL of N-methylpyrrolidone and 25 mL of toluene into a three-necked flask, and successively add 0.07 - 0.1 mol of 1-(3-allyl-2,4-dihydroxyphenyl)ethanone, 0.01 - 0.04 mol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.08 - 0.2 mol of 4,4'-dichlorodiphenyl sulfone, and 0.1 - 0.2 mol of anhydrous potassium carbonate. Then add a certain amount of toluene to the water separator to make its liquid level flush with the neck of the water separator. Turn on the electric heating mantle and slowly heat up to 140 °C. After dehydration for 3 h, drain the water and toluene in the water separator together and keep the water separator switch open. When the system temperature reaches 190 °C, continue the reaction for 5 h. After polymerization, pour it into a large amount of water for precipitation, then crush it and acidify it with dilute hydrochloric acid to remove excessive anhydrous potassium carbonate, incompletely reacted small molecules and oligomers. Filter to obtain the solid, and dry it in vacuum at 100 °C for 12 h.

7. A transparent multifunctional epoxy resin composite according to claim 1, characterized in that The curing agent is MHHPA.

8. A preparation method of a transparent multifunctional epoxy resin composite material, characterized in that, It includes the following preparation steps: Mix the silane coupling agent, solvent, aluminum silicate nanoflour, and zinc oxide, stir at 60 °C and 80 rpm for 30 min, then add the low-dielectric polymer, epoxy resin, and dispersant, continue to stir evenly, add the curing agent and AIBN, and carry out curing treatment.

9. The preparation method of a transparent multifunctional epoxy resin composite material according to claim 1, characterized in that, The curing treatment is as follows: Pour it into a mold preheated at 80 °C, cure at 80 °C for 1 h, then raise the temperature to 130 - 140 °C and cure for 4 h, and then raise the temperature to 150 - 200 °C and cure for 2 h.

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