A transparent multifunctional epoxy resin composite material and a preparation method thereof

Abstract

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

Description

Technical Field

[0001] This invention relates to the field of polymer compound materials technology, specifically to a transparent multifunctional epoxy resin composite material and its preparation method. Background Technology

[0002] In today's society, with the rapid development of information technology, the speed of information processing and dissemination is becoming increasingly faster. To adapt to this trend, electronic products are constantly evolving towards thinner, lighter, smaller, and more multifunctional designs. This trend has led to a significant increase in the density of internal components in electronic products, resulting in problems such as signal transmission delay, increased crosstalk noise, and increased power consumption. Among these problems, signal delay is particularly prominent, thus creating 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 speed of signal propagation is directly related to the dielectric constant of the substrate material; the lower the dielectric constant, the faster the signal propagation.

[0003] In today's industry, epoxy resin, polyimide resin, and polytetrafluoroethylene (PTFE) are three common resin choices for printed circuit board (PCB) substrate materials. PTFE is highly regarded for its excellent dielectric properties; however, it also has some significant drawbacks: poor processability, less than ideal mechanical and adhesive properties, and relatively high cost. While polyimide resin performs well in some aspects, its processing and molding are difficult, and its overall performance is not satisfactory. In contrast, epoxy resin is favored due to its wide availability of raw materials, low price, and ease of processing. After curing, epoxy resin exhibits excellent physicochemical properties, including good solvent resistance, low linear expansion, high mechanical strength, excellent thermal stability and dielectric properties, as well as resistance to surface leakage and arcing, making it the preferred choice for PCB composite materials. However, with the rapid development of microelectronics technology, the dielectric properties of pure epoxy resin can no longer meet the stringent 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 urgently needs to be addressed by current research and industry. Summary of the Invention

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

[0005] To address the aforementioned technical problems, this invention provides a transparent, multifunctional epoxy resin composite material, which is composed of the following components:

[0006]

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

[0008] Furthermore, the solvent is xylene.

[0009] Furthermore, the dispersant is a polyoxyethylene alkyl ether or sodium dodecylbenzene sulfonate.

[0010] Furthermore, the silane coupling agent is a coupling agent containing double bonds.

[0011] Further, the preparation method of the low-dielectric polymer is as follows: 75 mL of N-methylpyrrolidone and 25 mL of toluene are poured into a three-necked flask, and 0.07–0.1 mol of 1-(3-allyl-2,4-dihydroxyphenyl) ethyl ketone, 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 are added sequentially. Then, a certain amount of toluene is added. Add the liquid to the separator until the liquid level is flush with the neck of the separator. Turn on the electric heating mantle and slowly raise the temperature to 140°C. After dehydration for 3 hours, release the water and toluene from the separator together, and keep the separator switch open. When the system temperature reaches 190°C, continue the reaction for 5 hours. After the polymerization is complete, pour it into a large amount of water for precipitation. Then, crush it and acidify it with dilute hydrochloric acid to remove excess anhydrous potassium carbonate, unreacted small molecules and oligomers. Filter to obtain the solid and dry it under vacuum at 100°C for 12 hours.

[0012] Furthermore, the curing agent is MHHPA.

[0013] On the other hand, the present invention provides a method for preparing a transparent multifunctional epoxy resin composite material, comprising the following preparation steps: mixing silane coupling agent, solvent, aluminum silicate nanopowder and zinc oxide, stirring at 60°C and 80 rpm for 30 min, adding low dielectric polymer, epoxy resin and dispersant, continuing to stir evenly, adding curing agent and AIBN, and performing curing treatment.

[0014] Furthermore, the curing process is as follows: pour the mixture into a mold preheated at 80°C, cure at 80°C for 1 hour, then raise the temperature to 130-140°C and cure for 4 hours, then raise the temperature to 150-200°C and cure for 2 hours.

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

[0016] (1) This invention prepares a low dielectric constant polymer by polymerizing 1-(3-allyl-2,4-dihydroxyphenyl) ethyl ketone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 4,4′-dichlorodiphenyl sulfone. Since the two trifluoromethyl groups are 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 greatly reduced, which effectively reduces the dielectric constant of the polymer. The components in the epoxy resin composite material are optimized to effectively reduce the dielectric loss of the epoxy resin. In addition, this invention also adds zinc oxide and aluminum silicate nanopowder. The above materials have low dielectric constant and dielectric loss, which optimizes the dielectric properties of the epoxy resin composite material.

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

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

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1

[0021] A transparent, multifunctional epoxy resin composite material, comprising the following components:

[0022]

[0023]

[0024] The preparation method of the low dielectric polymer is as follows: 75 mL of N-methylpyrrolidone and 25 mL of toluene are poured into a three-necked flask, and 0.07 mol of 1-(3-allyl-2,4-dihydroxyphenyl) ethyl ketone, 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 are added in sequence. Then, a certain amount of toluene is added to the water separator so that the liquid level is level with the neck of the water separator. The electric heating mantle is turned on and the temperature is slowly raised to 140°C. After dehydration for 3 hours, the water and toluene in the water separator are released together, and the water separator switch is kept open. When the system temperature reaches 190°C, the reaction continues for 5 hours. After the polymerization is completed, it is poured into a large amount of water for precipitation. Then, it is crushed and acidified with dilute hydrochloric acid to remove excess anhydrous potassium carbonate, unreacted small molecules and oligomers. The solid is filtered and dried under vacuum at 100°C for 12 hours.

[0025] The transparent multifunctional epoxy resin composite material includes the following preparation steps: silane coupling agent, solvent, aluminum silicate nanopowder with a particle size of 50 nm, and zinc oxide with a particle size of 50 nm are mixed and stirred at 60°C and 80 rpm for 30 min. Then, low dielectric polymer, epoxy resin, and dispersant are added, and stirring is continued until uniform. A curing agent is added to obtain a polymer compound material solution. The polymer compound material solution and AIBN are mixed at a mass ratio of 100:5 and poured into a mold preheated at 80°C. After curing at 80°C for 1 h, the temperature is raised to 130°C and cured for 4 h. Then, the temperature is raised to 150°C and cured for 2 h.

[0026] Example 2

[0027] A transparent, multifunctional epoxy resin composite material, comprising the following components:

[0028]

[0029]

[0030] The preparation method of the low-dielectric polymer is as follows: 75 mL of N-methylpyrrolidone and 25 mL of toluene are poured into a three-necked flask, and 0.075 mol of 1-(3-allyl-2,4-dihydroxyphenyl) ethyl ketone and 0.02 mol of... are added sequentially. 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.09 mol 4,4′-dichlorodiphenyl sulfone, and 0.12 mol anhydrous potassium carbonate were mixed. Then, a certain amount of toluene was added to the water separator, making the liquid level level with the neck of the water separator. The electric heating mantle was turned on and the temperature was slowly raised to 140°C. After dehydration for 3 hours, the water and toluene in the water separator were released together, and the water separator switch was kept open. When the system temperature reached 190°C, the reaction continued for 5 hours. After the polymerization was completed, the mixture was poured into a large amount of water for precipitation. The precipitate was then crushed and acidified with dilute hydrochloric acid to remove excess anhydrous potassium carbonate, unreacted small molecules and oligomers. The solid was filtered and dried under vacuum at 100°C for 12 hours.

[0031] The epoxy resin composite material comprises the following preparation steps: silane coupling agent, solvent, aluminum silicate nanopowder with a particle size of 50 nm, and zinc oxide with a particle size of 50 nm are mixed and stirred at 60°C and 80 rpm for 30 min. Then, low dielectric polymer, epoxy resin, and dispersant are added, and stirring is continued until uniform. A curing agent is added to obtain a polymer compound material solution. The polymer compound material solution and AIBN are mixed at a mass ratio of 100:5 and poured into a mold preheated at 80°C. After curing at 80°C for 1 h, the temperature is raised to 135°C and cured for 4 h. Then, the temperature is raised to 160°C and cured for 2 h.

[0032] Example 3

[0033] A transparent, multifunctional epoxy resin composite material, comprising the following components:

[0034]

[0035] The preparation method of the low-dielectric polymer is as follows: 75 mL of N-methylpyrrolidone and 25 mL of toluene are poured into a three-necked flask, and 0.09 mol of 1-(3-allyl-2,4-dihydroxyphenyl) ethyl ketone and 0.03 mol of... are added sequentially. 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.1 mol 4,4′-dichlorodiphenyl sulfone, and 0.1–0.2 mol anhydrous potassium carbonate were mixed. Then, a certain amount of toluene was added to the water separator until the liquid level was flush with the neck of the separator. The electric heating mantle was turned on and the temperature was slowly raised to 140°C. After dehydration for 3 hours, the water and toluene in the water separator were released together, and the water separator switch was kept open. When the system temperature reached 190°C, the reaction continued for 5 hours. After polymerization was completed, the mixture was poured into a large amount of water for precipitation. The precipitate was then crushed and acidified with dilute hydrochloric acid to remove excess anhydrous potassium carbonate, unreacted small molecules and oligomers. The solid was filtered and dried under vacuum at 100°C for 12 hours.

[0036] The epoxy resin composite material comprises the following preparation steps: silane coupling agent, solvent, aluminum silicate nanopowder with a particle size of 50 nm, and zinc oxide with a particle size of 50 nm are mixed and stirred at 60°C and 80 rpm for 30 min. Then, low dielectric polymer, epoxy resin, and dispersant are added, and stirring is continued until uniform. A curing agent is added to obtain a polymer compound material solution. The polymer compound material solution and AIBN are mixed at a mass ratio of 100:5 and poured into a mold preheated at 80°C. After curing at 80°C for 1 h, the temperature is raised to 140°C and cured for 4 h. Then, the temperature is raised to 180°C and cured for 2 h.

[0037] Example 4

[0038] A transparent, multifunctional epoxy resin composite material, comprising the following components:

[0039]

[0040] The preparation method of the low dielectric polymer is as follows: 75 mL of N-methylpyrrolidone and 25 mL of toluene are poured into a three-necked flask, and 0.1 mol of 1-(3-allyl-2,4-dihydroxyphenyl) ethyl ketone, 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 are added in sequence. Then, a certain amount of toluene is added to the water separator so that the liquid level is level with the neck of the water separator. The electric heating mantle is turned on and the temperature is slowly raised to 140°C. After dehydration for 3 hours, the water and toluene in the water separator are released together, and the water separator switch is kept open. When the system temperature reaches 190°C, the reaction continues for 5 hours. After the polymerization is completed, it is poured into a large amount of water for precipitation. Then, it is crushed and acidified with dilute hydrochloric acid to remove excess anhydrous potassium carbonate, unreacted small molecules and oligomers. The solid is filtered and dried under vacuum at 100°C for 12 hours.

[0041] The epoxy resin composite material comprises the following preparation steps: silane coupling agent, solvent, aluminum silicate nanopowder with a particle size of 50 nm, and zinc oxide with a particle size of 50 nm are mixed and stirred at 60°C and 80 rpm for 30 min. Then, low dielectric polymer, epoxy resin, and dispersant are added, and stirring is continued until homogeneous. A curing agent is added to obtain a polymer compound material solution. The polymer compound material solution and AIBN are mixed at a mass ratio of 100:5 and poured into a mold preheated at 80°C. After curing at 80°C for 1 h, the temperature is raised to 140°C and cured for 4 h. Then, the temperature is raised to 200°C and cured 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; the remaining steps are the same as in Example 1.

[0044] Comparative Example 2

[0045] The difference between Comparative Example 2 and Example 1 is that allyl dimethoxysilane is not added, while the other steps are the same as in Example 1.

[0046] Comparative Example 3

[0047] The difference between Comparative Example 3 and Example 1 is that aluminum silicate nanopowder is not added, while the other steps are the same as in Example 1.

[0048] Comparative Example 4

[0049] The difference between Comparative Example 4 and Example 1 is that zinc oxide is not added; the remaining steps are the same as in Example 1.

[0050] Example of effect

[0051] Table 1 below shows 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.

[0052] Table 1

[0053]

[0054]

[0055] This invention synthesizes a low-dielectric-constant polymer by polymerizing 1-(3-allyl-2,4-dihydroxyphenyl)ethyl ketone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 4,4′-dichlorodiphenyl sulfone. Due to the close proximity of the two trifluoromethyl groups and their strong electron-withdrawing ability, charge transfer within the structural units and the formation of charge-transfer complexes in the molecule are significantly reduced, effectively lowering the polymer's dielectric constant. The components in the epoxy resin composite material are optimized to effectively reduce the dielectric loss of the epoxy resin. Furthermore, this invention additionally incorporates zinc oxide and aluminum silicate nanoparticles, which possess low dielectric constants and dielectric losses, thus optimizing the dielectric properties of the epoxy resin composite material. This invention also utilizes the chemical reaction between the low-dielectric-constant polymer, epoxy resin, and silane coupling agent to form strong chemical bonds, significantly improving the mechanical strength of the epoxy resin composite material, forming a dense interfacial layer, reducing bubbles and defects, and enhancing the reliability of the epoxy resin composite material. In addition, epoxy resin, silane coupling agent, aluminum silicate nanopowder, and zinc oxide are chemically bonded together, giving epoxy resin composites excellent moisture resistance, improving their reliability in harsh environments, and extending their service life.

[0056] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A transparent multifunctional epoxy resin composite material, characterized by, The epoxy resin composite is composed of the following components: Low dielectric polymer 18-30 parts by weight; Epoxy resin 30-50 parts by weight; Silane coupling agent 5-10 parts by weight; Aluminum silicate nano powder 5-10 parts by weight; Solvent 50-80 parts by weight; Dispersing agent 1-5 parts by weight; Zinc oxide 2-8 parts by weight Curing agent 10-15 parts by weight; The epoxy resin is a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, with an epoxy equivalent weight of 180-250 g / eq; The solvent is xylene; the dispersing agent is polyoxyethylene alkyl ether or sodium dodecylbenzenesulfonate; the silane coupling agent is a double bond-containing coupling agent; The preparation method of the low dielectric polymer is as follows: 75 mL of N-methylpyrrolidone and 25 mL of toluene are poured into a three-necked flask, 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 are added in sequence, then a certain amount of toluene is added to the water trap so that the liquid level is flush with the neck of the water trap, the electric heating jacket is turned on and slowly heated to 140℃, and dehydrated for 3h, then the water and toluene in the water trap are discharged together, and the water trap switch is kept open, when the system temperature reaches 190℃, continue to react for 5h, after the polymerization is completed, pour into a large amount of water for precipitation, then crush and acidify with dilute hydrochloric acid to remove excess anhydrous potassium carbonate, unreacted small molecules and oligomers, filter the solid, and dry at 100℃ under vacuum for 12h; The curing agent is MHHPA; The preparation method of the transparent multifunctional epoxy resin composite material includes the following preparation steps: mixing the silane coupling agent, solvent, aluminum silicate nano powder, and zinc oxide, stirring at 60℃ and 80rpm for 30min, then adding the low dielectric polymer, epoxy resin, and dispersing agent, continuing to stir uniformly, adding the curing agent, and obtaining a high molecular compound material solution, mixing the high molecular compound material solution and AIBN according to a mass ratio of 100:5, and performing curing treatment; The curing treatment is as follows: pour into a preheated mold at 80℃, cure at 80℃ for 1h, then heat to 130-140℃, cure for 4h, and then heat to 150-200℃, and cure for 2h.

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