Cardanol type dicyclopentadiene phenolic resin as well as preparation method and application thereof

Abstract

The invention relates to the technical field of phenolic resin synthesis, in particular to cardanol type dicyclopentadiene phenolic resin as well as a preparation method and application thereof. The cardanol type dicyclopentadiene phenolic resin has a molecular structure as shown in a formula 1, and in the formula 1, an R1 group is at least one of H,-CH3,-CH2CH3 and the like; the polymerization degree n1 is 0 to 13. According to the cardanol type dicyclopentadiene phenolic resin, the high-performance electronic base resin with heat resistance, mechanical property and dielectric property is successfully prepared on the premise of being green and environment-friendly through a combination strategy of natural raw material replacement, structure and function integrated design, multi-performance synergistic realization, simple process and wide application; and a new way is provided for sustainable development of electronic materials.

Description

Technical Field

[0001] This application relates to the field of phenolic resin synthesis technology, and in particular to a cashew phenolic resin of dicyclopentadiene and its preparation method and application. Background Technology

[0002] With the accelerating pace of industrialization, the emissions of industrial waste have continued to increase, leading to increasingly severe global environmental pollution and extreme climate problems. The introduction of environmental protection policies and the growing emphasis on environmental awareness in the manufacturing industry have prompted a shift towards green electronic materials. The environmental compatibility of electronic materials emphasizes that their environmental friendliness must be considered throughout the entire process from design, manufacturing, use to disposal. Therefore, natural materials can be considered as a research direction for green electronic materials at this stage.

[0003] However, the field of electronic materials still relies heavily on petroleum-based raw materials. While natural materials have environmentally friendly potential, their limited market availability and high cost pose significant challenges to the greening and carbon neutrality of electronic materials. Furthermore, natural materials suffer from insufficient purity, and their complex chemical structures often prevent electronic materials prepared from them from achieving the superior performance of mature industrialized petroleum-based resins. Even when natural materials can be synthesized into high-performance electronic base resins, these processes are generally demanding and complex, deviating from carbon neutrality goals in terms of energy consumption and emissions. Moreover, the performance of electronic base resins formed from natural materials is generally poor, failing to meet the requirements of electronic materials applications. Therefore, due to these constraints, natural material-based resins are still unable to replace petroleum-based electronic resins in electronic material applications. Summary of the Invention

[0004] This application provides a cashew phenol-type dicyclopentadiene phenolic resin, its preparation method, and its application, in order to solve the following technical problem: how to prepare high-performance electronic base resin under green and environmentally friendly conditions.

[0005] In a first aspect, embodiments of this application provide a cashew phenol-type dicyclopentadiene phenolic resin, wherein the cashew phenol-type dicyclopentadiene phenolic resin has a molecular structure as shown in Formula 1. Formula 1, In Formula 1, the R1 group is H, -CH3, -CH2CH3, and At least one of them; the degree of polymerization n1 is 0 to 13.

[0006] Optionally, the equivalent amount of hydroxyl groups in the cashew phenol-type dicyclopentadiene phenolic resin is from 256 g / eq to 330 g / eq.

[0007] Secondly, embodiments of this application provide a method for preparing the cashew phenol-type dicyclopentadiene phenolic resin described in the first aspect, the method comprising: Dicyclopentadiene, cashew phenol, and the first catalyst are subjected to a first catalytic reaction to obtain the first reaction product; The first reaction product was subjected to a first purification treatment using a first solvent to obtain a cashew nut shell extract intermediate; wherein the cashew nut shell extract intermediate has a molecular structure as shown in Formula 2. , Formula 2; The monophenol compound, the second catalyst, and the cashew phenol intermediate are subjected to a second catalytic reaction to obtain a second reaction product. The second reaction product was purified using a small amount of material and a second solvent to obtain a cashew phenol-type dicyclopentadiene phenolic resin.

[0008] Optionally, the amount of dicyclopentadiene n1 and the amount of cashew phenol n2 satisfy: n1:n2=1:(0.25 to 1.00); and / or The amount of the first catalyst is 0.01% to 0.07% of the amount of cashew phenol; and / or The mass m1 of the cashew phenol intermediate and the mass m2 of the monophenol compound satisfy: m1:m2=100:(80 to 150); and / or The mass m3 of the second catalyst and the mass m1 of the cashew phenol intermediate satisfy: m3:m1 = (0.40 to 1.80):100; and / or The mass m4 of the small material and the mass m1 of the cashew phenol intermediate satisfy the following condition: m4:m1 = (0.14 to 0.80):100.

[0009] Optionally, the first catalyst may include at least one of boron trifluoride diethyl ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid; and / or The first solvent includes at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone, and ethyl acetate; and / or The monophenolic compounds include at least one of phenol, p-cresol, p-ethylphenol, p-octylphenol, and p-tert-octylphenol; and / or The second catalyst includes at least one of the following: methanesulfonic acid, boron trifluoride diethyl ether, boron trifluoride methanol, dimethylsulfonic acid, hydrochloric acid, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid; and / or The types of the small materials include at least one of sodium bicarbonate, sodium carbonate, sodium phosphate, potassium carbonate, magnesium oxide, calcium oxide, calcium hydroxide, and magnesium carbonate; and / or The second solvent includes at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone, and ethyl acetate.

[0010] Optionally, the temperature of the first catalytic reaction is 55°C to 90°C, and the time of the first catalytic reaction is 5 hours to 36 hours; and / or The temperature of the second catalytic reaction is 90°C to 120°C, and the time of the second catalytic reaction is 3 hours to 8 hours.

[0011] Thirdly, embodiments of this application provide an epoxy derivative of a cashew phenol-type dicyclopentadiene phenolic resin, wherein the raw material for the epoxy derivative includes the cashew phenol-type dicyclopentadiene phenolic resin described in the first aspect, and the derivative has a molecular structure as shown in Formula 3. , Formula 3, In Formula 3, R1 group is H, -CH3, -CH2CH3, and At least one of the following; the degree of polymerization n2 is 0 to 21; The equivalent amount of epoxy molecules in the epoxy derivative is from 297 g / eq to 366 g / eq.

[0012] Fourthly, embodiments of this application provide a method for preparing the epoxy derivative described in the third aspect, the method comprising: Epichlorohydrin, a third catalyst, and the cashew nut shell phenolic resin described in the first aspect are subjected to a third catalytic reaction to obtain a third catalytic product; wherein the temperature of the third catalytic reaction is 60°C to 90°C, and the time of the third catalytic reaction is 1 h to 5 h; the mass m5 of the cashew nut shell phenolic resin and the mass m6 of the epichlorohydrin satisfy the following ratio: m5:m6 = 100:(180 to 340); the mass m7 of the third catalyst and the mass m5 of the cashew nut shell phenolic resin satisfy the following ratio: m7:m5 = (59.0 to 67.7):100; The third catalytic product was purified using a third solvent to obtain an epoxy derivative of cashew phenol-type dicyclopentadiene phenolic resin. The third catalyst includes at least one of triethylamine, ammonia, sodium silicate, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; and / or The third solvent includes at least one of toluene, xylene, methyl isobutyl ketone, and ethyl acetate.

[0013] Fifthly, embodiments of this application provide a composition for copper-clad laminates, comprising, by mass parts, an active component and a solvent, wherein the mass of the active component is 77.06% to 86.42% of the mass of the composition; the raw materials of the active component include, by mass parts of the epoxy derivative described in the third aspect (hydroxyl equivalent): 150 to 200 parts, an active ester resin: 20 to 50 parts, a phosphorus-containing phenolic resin: 80 to 95 parts, and an imidazole catalyst: 2 to 5 parts; and the active solvent is 55 to 75 parts by mass.

[0014] Sixthly, embodiments of this application provide a method for preparing a resin-clad copper laminate, the method comprising: The composition described in the fifth aspect is impregnated onto the surface of a fiberglass cloth to obtain an impregnated fiberglass cloth. The impregnated fiberglass cloth is dried to obtain prepolymer fiberglass cloth; The multilayer prepolymer fiberglass cloth is stacked to obtain a laminated fiberglass cloth; Copper foil is adhered to both ends of the laminated fiberglass cloth and then vacuum hot-pressed to obtain a resin-coated copper plate.

[0015] The technical solutions provided in this application have the following advantages compared with the prior art: This application provides a cashew nut shell oil-derived dicyclopentadiene phenolic resin. This resin uses cashew nut shell oil as its core raw material, and through the reaction between cashew nut shell oil and dicyclopentadiene, a cashew nut shell oil-derived dicyclopentadiene phenolic resin product rich in various rigid aromatic groups and flexible alkyl chains is formed. The rigid aromatic groups in this cashew nut shell oil-derived dicyclopentadiene phenolic resin can improve its heat resistance, mechanical strength, and dielectric properties. Simultaneously, the flexible alkyl chains in this cashew nut shell oil-derived dicyclopentadiene phenolic resin can endow it with self-toughening properties without the need for additional toughening agents, achieving structural self-reinforcement under green and environmentally friendly conditions. Therefore, high-performance electronic base resins can be prepared under green and environmentally friendly conditions. Attached Figure Description

[0016] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.

[0017] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a schematic flowchart of a method for preparing cashew phenol-type dicyclopentadiene phenolic resin provided in an embodiment of this application; Figure 2 This is a schematic flowchart of a method for preparing epoxy derivatives provided in an embodiment of this application; Figure 3 This is a schematic diagram of a method for preparing a resin-coated copper board according to an embodiment of this application. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0020] The range descriptions used in this application, such as numerical ranges and proportional ranges, include all possible sub-ranges and single numerical values ​​within that range. For example, the range descriptions of "1 to 6" or "1~6" cover all sub-ranges (such as 1 to 3, 2 to 5, etc.) and single numbers (such as 1, 2, 3, 4, 5, 6) between 1 and 6. Unless otherwise specified, the terms "comprising" and others used herein mean "including but not limited to"; relational terms such as "first" and "second" are used only to distinguish different entities or operations and do not imply an actual order or relationship; "and / or" indicates that multiple situations can exist individually or simultaneously; expressions such as "at least one," "multiple," and "at least one" refer to any combination of the corresponding objects, including combinations of single or multiple objects. The proportional relationships involved in this document, such as mass ratios and molar ratios, should be understood as the correspondence between the first and second terms of a proportional formula, according to the order of description. The raw materials, reagents, instruments, and equipment used herein can all be obtained by purchasing from the market or by existing methods.

[0021] This application provides a cashew phenol-type dicyclopentadiene phenolic resin, which has a molecular structure as shown in Formula 1. , Formula 1, In Formula 1, the R1 group is H, -CH3, -CH2CH3, and At least one of them; the degree of polymerization n1 is 0 to 13.

[0022] The degree of polymerization n1 can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13.

[0023] It should be noted that the cashew phenol type dicyclopentadiene phenolic resin is a brownish-red or brownish-black solid.

[0024] It should be noted that the cashew nut shell phenolic resin provided in this application embodiment is a high-performance electronic base resin prepared under green and environmentally friendly conditions through four dimensions: raw material selection, structural design, performance realization, and process. The specific mechanism is as follows: 1. Green raw materials: based on natural and renewable resources.

[0025] Using cashew phenol as one of the core raw materials, cashew phenol is a natural green product derived from cashew shell oil. It is a renewable resource that replaces traditional petroleum-based chemical raw materials. This realizes the green attributes of cashew phenol-type dicyclopentadiene phenolic resin materials from the source, which is in line with the trend of sustainable development and green chemistry.

[0026] 2. Structural design: combining rigidity and flexibility to balance performance and environmental protection.

[0027] The molecular structure of cashew phenol-type dicyclopentadiene phenolic resin integrates various rigid aromatic groups (such as benzene rings, pentane rings of dicyclopentadiene, or cyclohexane rings) with the flexible alkyl chain of cashew phenol. (1) Rigid groups: ensure that cashew phenol type dicyclopentadiene phenolic resin has high heat resistance, high mechanical strength and high dielectric properties.

[0028] (2) Flexible alkyl chain: The flexible alkyl chain of cashew phenol can give cashew phenol-type dicyclopentadiene phenolic resin a self-toughening property, which can greatly improve the impact resistance of cashew phenol-type dicyclopentadiene phenolic resin. No additional toughening agent is needed, which reduces the pollution and process complexity of toughening agent and realizes the environmentally friendly design of self-reinforcing structure.

[0029] 3. Performance realization: Multi-dimensional high performance meets the needs of the electronics field.

[0030] (1) Thermal properties: The glass transition temperature (DMA) reaches 178℃ to 225℃, the thermal delamination time T300>60min, and the copper-coated soldering resistance time>300s, which meets the stringent requirements of electronic materials for high temperature stability.

[0031] (2) Dielectric properties: low dielectric constant and dielectric loss, suitable for the signal transmission requirements of high-frequency electronic devices (such as 5G, high-speed circuit boards).

[0032] (3) Mechanical properties: The synergistic effect of the rigid skeleton and the flexible chain ensures that the cashew phenol type dicyclopentadiene phenolic resin material has sufficient mechanical strength and can be used for electronic components with high mechanical performance requirements such as copper clad laminates.

[0033] 4. Process and application: Simple preparation and wide range of applications; green and efficient.

[0034] (1) Preparation process: The method is simple and practical, without the need for complex and highly polluting processes, which reduces the environmental burden of the production process and embodies the concept of green preparation.

[0035] (2) Application scenarios: It is not limited to copper clad laminates, but is also applicable to a variety of electronic components, realizing multiple uses of one material, improving resource utilization efficiency, and conforming to the high efficiency principle of green chemical industry.

[0036] In summary, the cashew phenol-type dicyclopentadiene phenolic resin provided in this application provides a high-performance electronic base resin with heat resistance, mechanical properties, and dielectric properties through a combination strategy of natural raw material substitution, integrated structural and functional design, synergistic realization of multiple properties, simple process, and wide application, under the premise of green and environmental protection. This provides a new approach for the sustainable development of electronic materials.

[0037] In some alternative embodiments, the equivalent of hydroxyl groups in the cashew phenol-type dicyclopentadiene phenolic resin is from 256 g / eq to 330 g / eq.

[0038] In these embodiments, the presence of hydroxyl groups in the cashew phenol-type dicyclopentadiene phenolic resin at an equivalent of 256 g / eq to 330 g / eq indicates that the cashew phenol-type dicyclopentadiene phenolic resin has sufficient hydroxyl groups. Sufficient hydroxyl groups are beneficial to the subsequent epoxidation third catalytic reaction, allowing the cashew phenol-type dicyclopentadiene phenolic resin to be more fully converted into the epoxy derivative of the cashew phenol-type dicyclopentadiene phenolic resin, thereby increasing the number of rigid groups in the epoxy derivative and improving its performance.

[0039] In cashew phenol-type dicyclopentadiene phenolic resins, the equivalent of the hydroxyl group can be 256 g / eq, 258 g / eq, 260 g / eq, 265 g / eq, 270 g / eq, 280 g / eq, 290 g / eq, 300 g / eq, 310 g / eq, 320 g / eq, or 330 g / eq.

[0040] It should be noted that the hydroxyl equivalent (eq) refers to the epoxy equivalent weight (EEW). EEW is an indicator describing the content of epoxy-related groups in epoxy resins, usually expressed in grams per equivalent (g / eg) or grams per mole (g / mol). Epoxy equivalent generally signifies the density of epoxy-related groups. The lower the epoxy equivalent, the higher the density of epoxy groups, resulting in a greater crosslinking density in the cured product. Consequently, the physical and mechanical properties and chemical resistance of the epoxy resin will be correspondingly improved.

[0041] Figure 1 An exemplary schematic diagram of a method for preparing cashew phenol-type dicyclopentadiene phenolic resin according to an embodiment of this application is shown. Based on a general inventive concept, such as Figure 1 As shown in the embodiments of this application, a method for preparing the cashew phenol-type dicyclopentadiene phenolic resin is provided, the method comprising: S1. Dicyclopentadiene, cashew phenol and the first catalyst are subjected to a first catalytic reaction to obtain the first reaction product; S2. The first reaction product is subjected to a first purification treatment using a first solvent to obtain a cashew nut shell intermediate; wherein the cashew nut shell intermediate has a molecular structure as shown in Formula 2. , Formula 2; S3. The monophenol compound, the second catalyst, and the cashew phenol intermediate are subjected to a second catalytic reaction to obtain the second reaction product; S4. The second reaction product is purified using a small amount of material and a second solvent to obtain cashew phenol type dicyclopentadiene phenolic resin.

[0042] This method is for preparing the above-mentioned cashew phenol type dicyclopentadiene phenolic resin. The specific structure of the cashew phenol type dicyclopentadiene phenolic resin can be referred to the above embodiments. Since this method adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be elaborated here.

[0043] It should be noted that, under the catalysis of the first catalyst, a nucleophilic substitution reaction occurs between dicyclopentadiene and cashew phenol, forming a cashew phenol intermediate with a dicyclopentadiene group and a cashew phenol backbone. Subsequently, under the catalysis of the second catalyst, a series of nucleophilic substitution and polymerization reactions occur between the monophenol compound and the cashew phenol intermediate, yielding the target product, a cashew phenol-type dicyclopentadiene phenolic resin.

[0044] It should be noted that the first catalytic reaction can be carried out in a 5L reaction flask equipped with a nitrogen inlet / outlet, a stirrer, a temperature sensor (or thermometer), and a reflux condenser. The first catalytic reaction must be carried out under a nitrogen atmosphere. After the first catalytic reaction is completed, the reaction can continue for a period of time (generally 1 to 3 hours).

[0045] It should be noted that the first purification process can be as follows: after the first catalytic reaction is completed, a small amount of material can be added to the system of the first reaction product for neutralization, and then an appropriate amount of the first solvent can be added to dissolve the first reaction product and form a first reaction product solution system; the first reaction product solution system is heated to 60°C to 80°C, and then the first reaction product solution system is filtered while hot to obtain a pure first reaction product solution system; the pure first reaction product solution system is subjected to vacuum distillation to 190°C to 220°C and a vacuum degree ≥ -0.09 MPa until no other fractions are separated. The product obtained in the vacuum distillation apparatus is the cashew phenol intermediate.

[0046] It should be noted that in the second catalytic reaction, the monophenol compound and the cashew phenol intermediate are first mixed, and then the resulting mixture is heated to 50°C to 60°C before the second catalyst is added. The equipment used for this second catalytic reaction can be the same as that used for the first catalytic reaction.

[0047] It should be noted that the second purification process can be as follows: after the second catalytic reaction is completed, a small amount of material is added to the system of the second reaction product, and the mixture is stirred for 3 to 5 hours at the temperature of the second catalytic reaction. Then, an appropriate amount of the second solvent is added to dissolve the material and obtain the solution system of the second reaction product. The solution system of the second reaction product is heated to 190°C to 220°C and subjected to vacuum distillation until the vacuum degree is ≥-0.09 MPa and no distillate is distilled off, thus obtaining the target product, cashew phenol type dicyclopentadiene phenolic resin.

[0048] In some alternative embodiments, the amount n1 of the dicyclopentadiene and the amount n2 of the cashew phenol satisfy: n1:n2 = 1:(0.25 to 1.00); and / or The amount of the first catalyst is 0.01% to 0.07% of the amount of cashew phenol; and / or The mass m1 of the cashew phenol intermediate and the mass m2 of the monophenol compound satisfy: m1:m2=100:(80 to 150); and / or The mass m3 of the second catalyst and the mass m1 of the cashew phenol intermediate satisfy: m3:m1 = (0.40 to 1.80):100; and / or The mass m4 of the small material and the mass m1 of the cashew phenol intermediate satisfy the following condition: m4:m1 = (0.14 to 0.80):100.

[0049] In these embodiments, a molar ratio of dicyclopentadiene and cashew phenol of 1:(0.25 to 1.00) allows the first catalytic reaction to proceed sufficiently, forming a cashew phenol intermediate rich in dicyclopentadiene groups and a cashew phenol backbone. Furthermore, a first catalyst at a molar ratio of 0.01% to 0.07% of the cashew phenol ensures sufficient catalyst in the first catalytic reaction system, allowing for sufficient first catalytic reaction between dicyclopentadiene and cashew phenol to form a cashew phenol intermediate containing dicyclopentadiene groups and a cashew phenol backbone. Additionally, a mass ratio of cashew phenol intermediate to monophenol compound of 100:(80 to 150) allows the second catalytic reaction to proceed sufficiently, forming a second reaction product rich in the target product, a cashew phenol-type dicyclopentadiene phenolic resin. Furthermore, a mass ratio of the second catalyst to the cashew phenol intermediate of (0.40 to 1.80):100 ensures sufficient second catalyst in the second catalytic reaction system. Under the action of sufficient second catalyst, the cashew phenol intermediate and the monophenol compound can undergo a sufficient second catalytic reaction to form a second reaction product rich in the target product, cashew phenol-type dicyclopentadiene phenolic resin. Additionally, a mass ratio of the auxiliary material to the cashew phenol intermediate of (0.14 to 0.80):100 allows excess acidic components in the auxiliary material and the second reaction product to facilitate other steps in the second purification process, thereby improving the purity of the final target product, the cashew phenol-type dicyclopentadiene phenolic resin.

[0050] The amount of cashew phenol, n2, can be 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.60, 0.70, 0.80, 0.90, or 1.00.

[0051] The amount of the first catalyst may be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, or 0.07% of the amount of cashew phenol.

[0052] The mass m2 of the monophenol compound can be 80, 90, 100, 110, 120, 130, 140 or 150.

[0053] The mass m3 of the second catalyst can be 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.20, 1.40, 1.60 or 1.80.

[0054] The mass m4 of this small material can be 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70 or 0.80.

[0055] In some alternative embodiments, the first catalyst includes at least one selected from boron trifluoride diethyl ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid; and / or The first solvent includes at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone, and ethyl acetate; and / or The monophenolic compounds include at least one of phenol, p-cresol, p-ethylphenol, p-octylphenol, and p-tert-octylphenol; and / or The second catalyst includes at least one of the following: methanesulfonic acid, boron trifluoride diethyl ether, boron trifluoride methanol, dimethylsulfonic acid, hydrochloric acid, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid; and / or The types of the small materials include at least one of sodium bicarbonate, sodium carbonate, sodium phosphate, potassium carbonate, magnesium oxide, calcium oxide, calcium hydroxide, and magnesium carbonate; and / or The second solvent includes at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone, and ethyl acetate.

[0056] In these embodiments, a first catalyst comprising at least one of boron trifluoride diethyl ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid is used. The first catalyst facilitates the complete catalytic reaction, forming a cashew nutshell intermediate rich in dicyclopentadiene groups and the cashew nutshell backbone. Furthermore, a first solvent comprising at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone, and ethyl acetate is used to sufficiently dissolve the first reaction product, facilitating a thorough first purification process and forming a cashew nutshell intermediate of higher purity. Additionally, a monophenolic compound comprising at least one of phenol, p-cresol, p-ethylphenol, p-octylphenol, and p-tert-octylphenol can fully react with the cashew nutshell intermediate in a second catalytic reaction, forming a second reaction product rich in the target product, a cashew nutshell-type dicyclopentadiene phenolic resin. Furthermore, using a second catalyst including at least one of methanesulfonic acid, boron trifluoride diethyl ether, boron trifluoride methanol, dimethylsulfonic acid, hydrochloric acid, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid can ensure the complete catalytic reaction, forming a second reaction product rich in the target product, cashew nut shell phenolic resin. Additionally, using small components including sodium bicarbonate, sodium carbonate, sodium phosphate, potassium carbonate, magnesium oxide, calcium oxide, calcium hydroxide, and magnesium carbonate can effectively adjust the pH of the second reaction product, facilitating the second purification process and yielding high-purity cashew nut shell phenolic resin. Furthermore, using a second solvent including at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone, and ethyl acetate can fully dissolve the second reaction product, further facilitating the second purification process and forming high-purity cashew nut shell phenolic resin.

[0057] In some alternative embodiments, the temperature of the first catalytic reaction is 55°C to 90°C, and the reaction time is 5 h to 36 h; and / or The temperature of the second catalytic reaction is 90°C to 120°C, and the time of the second catalytic reaction is 3 hours to 8 hours.

[0058] In these embodiments, a first catalytic reaction at a temperature of 55°C to 90°C and a time of 5 h to 36 h allows for a sufficient reaction between dicyclopentadiene and cashew nut kernels to form a cashew nut kernel intermediate rich in dicyclopentadiene groups and the cashew nut kernel backbone. Furthermore, a second catalytic reaction at a temperature of 90°C to 120°C and a time of 3 h to 8 h allows for… The temperature of the first catalytic reaction can be 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃ or 90℃.

[0059] The time for the first catalytic reaction can be 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 17h, 18h, 19h, 20h, 25h, 30h, 35h or 36h.

[0060] The temperature of the second catalytic reaction can be 90℃, 95℃, 100℃, 105℃, 110℃, 115℃ or 120℃.

[0061] The second catalytic reaction can take 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours.

[0062] Based on a general inventive concept, embodiments of this application provide an epoxy derivative of a cashew phenol-type dicyclopentadiene phenolic resin. The raw material for the epoxy derivative includes the cashew phenol-type dicyclopentadiene phenolic resin described in the first aspect. The derivative has a molecular structure as shown in Formula 3. , Formula 3, In Formula 3, R1 group is H, -CH3, -CH2CH3, and At least one of the following; the degree of polymerization n2 is 0 to 21; The equivalent amount of epoxy molecules in the epoxy derivative is from 297 g / eq to 366 g / eq.

[0063] The epoxy derivative is based on the above-mentioned cashew phenol type dicyclopentadiene phenolic resin. The specific structure of the cashew phenol type dicyclopentadiene phenolic resin can be referred to the above embodiments. Since the epoxy derivative adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be elaborated here.

[0064] It should be noted that the epoxy derivative of this cashew phenol type dicyclopentadiene phenolic resin can be a brownish-red to brownish-black semi-solid or solid.

[0065] The degree of aggregation n2 can be 0, 1, 2, 3, 4, 5, 10, 15, 20 or 21.

[0066] It should be noted that in epoxy derivatives, an equivalent amount of 297 g / eq to 366 g / eq of epoxy molecules can give the epoxy derivative a high density of epoxy groups, which in turn gives the epoxy derivative high physical and mechanical properties as well as chemical corrosion resistance.

[0067] The equivalent amount of epoxy molecules in this epoxy derivative can be 297 g / eq, 298 g / eq, 299 g / eq, 300 g / eq, 305 g / eq, 310 g / eq, 320 g / eq, 330 g / eq, 340 g / eq, 350 g / eq, or 360 g / eq.

[0068] It's important to note that the equivalent weight (eq) of an epoxy molecule refers to the epoxy equivalent weight (EEW). EEW is an indicator describing the content of epoxy-related groups in epoxy resins, usually expressed in grams per equivalent (g / eg) or grams per mole (g / mol). Epoxy equivalent weight generally signifies the density of epoxy-related groups. The lower the epoxy equivalent weight, the higher the density of epoxy groups, resulting in a greater crosslinking density in the cured product. Consequently, the physical and mechanical properties and chemical resistance of the epoxy resin will be correspondingly improved.

[0069] Figure 2 An exemplary schematic diagram of a method for preparing epoxy derivatives provided in an embodiment of this application is shown; Based on a general inventive concept, such as Figure 2 As shown in the embodiments of this application, a method for preparing the epoxy derivative is provided, the method comprising: S1. Epichlorohydrin, a third catalyst, and the cashew nut shell phenolic resin are subjected to a third catalytic reaction to obtain a third catalytic product; wherein the temperature of the third catalytic reaction is 60°C to 90°C, and the time of the third catalytic reaction is 1 h to 5 h; the mass m5 of the cashew nut shell phenolic resin and the mass m6 of the epichlorohydrin satisfy the following ratio: m5:m6 = 100:(180 to 340); the mass m7 of the third catalyst and the mass m5 of the cashew nut shell phenolic resin satisfy the following ratio: m7:m5 = (59.0 to 67.7):100; S2. The third catalytic product is purified using a third solvent to obtain an epoxy derivative of cashew phenol-type dicyclopentadiene phenolic resin. The third catalyst includes at least one of triethylamine, ammonia, sodium silicate, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; and / or The third solvent includes at least one of toluene, xylene, methyl isobutyl ketone, and ethyl acetate.

[0070] This method is for preparing the above-mentioned epoxy derivative. The specific structure of the epoxy derivative can be referred to in the above embodiments. Since this method adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be elaborated here.

[0071] The temperature for the third catalytic reaction can be 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, or 92℃.

[0072] The time for the third catalytic reaction can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5.0h.

[0073] The mass m6 of the epichlorohydrin can be 180, 190, 200, 220, 240, 260, 280, 300, 320 or 340.

[0074] The mass m7 of the third catalyst can be 59.0, 59.5, 60.0, 61.0, 62.0, 63.0, 64.0, 65.0, 66.0, 67.0 or 67.7.

[0075] It should be noted that, under the action of the third catalyst, cashew phenol-type dicyclopentadiene phenolic resin and epichlorohydrin with a mass ratio of 100:(180 to 340) can fully undergo the third catalytic reaction and form epoxy derivatives rich in epoxy groups.

[0076] It should be noted that the reactor used for the third catalytic reaction can be the same as that used for the first catalytic reaction. In the third catalytic reaction, cashew phenol-type dicyclopentadiene phenolic resin and epichlorohydrin can be directly mixed first, and then the mixture can be heated to 35°C to 60°C to dissolve it, forming a resin solution; then, a third catalyst aqueous solution (mass concentration can be 20% to 50%) is added dropwise to the resin solution in a temperature-controlled manner, and the dropwise addition time is less than or equal to 2 hours, followed by stirring at the same temperature for 2 hours to 5 hours to form the third catalytic reaction system; the third catalytic reaction system is then heated to 60°C to 90°C for 1 hour to... After 5 hours, the third catalytic product was obtained. Then, the product was subjected to vacuum distillation at 80°C to 120°C to remove epichlorohydrin. After vacuum distillation to a vacuum degree ≥ -0.08 MPa, the vacuum product was obtained. An appropriate amount of the third solvent was added to the vacuum product for dissolution. The dissolved organic phase was then washed with water at 60°C to 70°C until neutral to obtain the water-washed product. The water-washed product was then subjected to vacuum distillation to distill off the solvent, yielding the epoxy derivative of the cashew phenol type dicyclopentadiene phenolic resin.

[0077] Based on a general inventive concept, embodiments of this application provide a composition for copper-clad laminates, comprising, by mass parts, an active component and a solvent, wherein the active component comprises 77.06% to 86.42% of the composition by mass; the raw materials of the active component include the epoxy derivative: 150 to 200 parts, the active ester resin: 20 to 50 parts, the phosphorus-containing phenolic resin: 80 to 95 parts, and the imidazole catalyst: 2 to 5 parts; the active solvent comprises 55 to 75 parts by mass.

[0078] The composition for copper clad laminates is based on the above-mentioned epoxy derivatives. The specific structure of the epoxy derivatives can be referred to in the above embodiments. Since the composition for copper clad laminates adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be elaborated here.

[0079] The mass of the active component can be 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, or 72.8% of the mass of the composition.

[0080] The mass fraction of the epoxy derivative can be 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, or 200 parts.

[0081] The mass fraction of the active ester resin can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts.

[0082] The mass fraction of the phosphorus-containing phenolic resin can be 80, 81, 82, 83, 84, 85, 90, or 95 parts.

[0083] The mass fraction of the active solvent can be 55, 56, 57, 58, 59, 60, 65, 70, or 75 parts.

[0084] It should be noted that in the composition for copper-clad laminates, the active ester resin is a compound with active ester groups. This active ester resin can be HPC-8000-65T active ester curing agent (DIC Corporation, Japan), or it can be DFE-617, DFE-617L, or DFE-618 (Sichuan Dongcai Technology Group Co., Ltd.), etc. The phosphorus-containing phenolic resin can be DFE-395 resin (Sichuan Dongcai Technology Group Co., Ltd.). The accelerator can be at least one of 4-dimethylaminopyridine, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), 2-(dimethylaminomethyl)phenol, and triphenylphosphine (TPP). The filler may be at least one of the following: silica, wollastonite powder, glass microspheres, amphibole powder, calcium carbonate powder, basalt powder, pyroxene powder, feldspar powder, reduced graphene, montmorillonite, magnesium oxide, aluminum oxide, mica powder, barium sulfate, kaolin, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, titanium dioxide, talc, and iron oxide.

[0085] It should be noted that the composition may also include an active solvent for dissolving the active component, which may be at least one of acetone, butanone, cyclohexanone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether, and propylene glycol methyl ether acetate.

[0086] Figure 3 An exemplary schematic diagram of a method for preparing a resin-clad copper plate according to an embodiment of this application is shown; Based on a general inventive concept, such as Figure 3 As shown in the embodiment of this application, a method for preparing a resin-clad copper board is provided, the method comprising: S1. Impregnate the composition onto the surface of fiberglass cloth to obtain impregnated fiberglass cloth; S2. Dry the impregnated fiberglass cloth to obtain prepolymer fiberglass cloth; S3. The multilayer prepolymer fiberglass cloth is stacked to obtain a laminated fiberglass cloth; S4. Copper foil is adhered to both ends of the laminated fiberglass cloth and vacuum hot-pressed to obtain a resin-coated copper plate.

[0087] The preparation method is based on the above composition. The specific composition of the composition can be referred to the above embodiments. Since the preparation method adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments, which will not be repeated here.

[0088] It should be noted that the drying process can be a combination of sun-drying and oven-drying, the oven-drying temperature can be between 120℃ and 165℃, and the oven-drying time can be between 3 minutes and 15 minutes.

[0089] It should be noted that the vacuum hot pressing process can be as follows: first, the temperature is increased to 170℃ to 180℃ at a rate of 2.5℃ / min to 5℃ / min, while the vacuum hot pressing pressure is increased from 0.5MPa to 4.0MPa to 4.5MPa at a rate of 0.1MPa / min. Finally, the vacuum hot pressing pressure is reduced to a vacuum degree of <50 torr, and then the temperature and pressure are maintained for 1 to 2 hours. Then, the temperature is increased to 170℃ to 230℃ and the pressure is maintained for 3 to 5 hours. Finally, the pressure is released and the vacuum hot pressing mold is cooled.

[0090] It should be noted that the fiberglass cloth can be at least one of the following models: 1080E, 2116, 2313, 3313, and 7628 (China Jushi Co., Ltd., China Southern Glass Holding Co., Ltd., and Jizhong Energy Group Co., Ltd.). The specific number of fiberglass cloth layers in this laminated fiberglass cloth can be determined according to the actual copper clad laminate model, and can range from 2 to 36 layers.

[0091] The present application is further illustrated below with reference to specific embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national / industry standards; if there is no corresponding national / industry standard, they are performed according to general international standards, conventional conditions, or conditions recommended by the manufacturer.

[0092] Example 1 A cashew phenol-type dicyclopentadiene phenolic resin has a molecular structure as shown in Formula 1. , Formula 1, in which the R1 group is H; the degree of polymerization n is 6.9 (average value calculated according to GPC).

[0093] The equivalent of hydroxyl groups in cashew phenol-type dicyclopentadiene phenolic resin is 258 g / eq.

[0094] like Figure 1 As shown, a method for preparing cashew phenol-type dicyclopentadiene phenolic resin includes: S1. Dicyclopentadiene, cashew phenol and the first catalyst are subjected to a first catalytic reaction to obtain the first reaction product; S2. The first reaction product is subjected to a first purification treatment using a first solvent to obtain a cashew nut shell intermediate; wherein the cashew nut shell intermediate has a molecular structure as shown in Formula 2. , Formula 2; S3. The monophenol compound, the second catalyst, and the cashew phenol intermediate are subjected to a second catalytic reaction to obtain the second reaction product; S4. The second reaction product is purified using a small amount of material and a second solvent to obtain cashew phenol-type dicyclopentadiene phenolic resin.

[0095] The amounts of dicyclopentadiene (n1) and cashew nut shell (n2) satisfy the following equation: n1:n2 = 1:0.30. The amount of the first catalyst is 0.05% of the amount of cashew phenol; The mass m1 of the cashew phenol intermediate and the mass m2 of the monophenol compound satisfy the following: m1:m2=100:150; The mass m3 of the second catalyst and the mass m1 of the cashew phenol intermediate satisfy the following condition: m3:m1=0.5:100; The mass m4 of the small component and the mass m1 of the cashew phenol intermediate satisfy the following condition: m4:m1=0.40:100.

[0096] In the first purification process, a small amount of material was first used for adjustment. The amount of material n3 and the amount of the first catalyst n4 satisfy the following ratio: n3:n4=1.5:1. After adding the material, the reaction continued for 1 hour.

[0097] The first catalyst is p-toluenesulfonic acid; The first solvent is methyl isobutyl ketone; The type of monophenol compound is phenol; The second catalyst is methanesulfonic acid; The ingredient is sodium bicarbonate; The second solvent includes at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone, and ethyl acetate.

[0098] The temperature of the first catalytic reaction is 70℃, and the time of the first catalytic reaction is 8h; The temperature of the second catalytic reaction is 100℃, and the time of the second catalytic reaction is 3h.

[0099] Example 2 Compared to Example 1, the differences in this example are as follows, while the rest are the same: In Formula 1, R1 group is of type H; degree of polymerization n is 6.7 (average value calculated according to GPC).

[0100] The mass m1 of the cashew phenol intermediate and the mass m2 of the monophenol compound satisfy the following equation: m1:m2=100:135.

[0101] The type of monophenol compound is phenol.

[0102] Example 3 Compared to Example 1, the differences in this example are as follows, while the rest are the same: In Formula 1, the R1 group is H; the degree of polymerization n is 8.1 (average value calculated according to GPC).

[0103] The mass m1 of the cashew phenol intermediate and the mass m2 of the monophenol compound satisfy the following equation: m1:m2=100:120.

[0104] The type of monophenol compound is phenol.

[0105] Example 4 Compared to Example 1, the differences in this example are as follows, while the rest are the same: In Formula 1, the R1 group is H; the degree of polymerization n is 10.3 (average value calculated according to GPC).

[0106] The mass m1 of the cashew phenol intermediate and the mass m2 of the monophenol compound satisfy the following condition: m1:m2=100:100.

[0107] The type of monophenol compound is phenol.

[0108] Example 5 Compared to Example 1, the differences in this example are as follows, while the rest are the same: In Formula 1, the R1 group is -CH3; the degree of polymerization n is 7.2 (average value calculated according to GPC).

[0109] The mass m1 of the cashew phenol intermediate and the mass m2 of p-cresol satisfy the following condition: m1:m2=91.9:100.

[0110] The monophenol compound is p-cresol.

[0111] Example 6 Compared to Example 1, the differences in this example are as follows, while the rest are the same: In Formula 1, the R1 group is The degree of polymerization, n, is 7.9 (average calculated based on GPC).

[0112] The mass m1 of the cashew phenol intermediate and the mass m2 of the monophenol compound satisfy the following equation: m1:m2 = 175.3:100.

[0113] The monophenol compound is p-tert-octylphenol.

[0114] Example 7 Compared to Example 1, the differences in this example are as follows, while the rest are the same: An epoxy derivative of a cashew phenol-type dicyclopentadiene phenolic resin, wherein the raw material for the epoxy derivative includes a cashew phenol-type dicyclopentadiene phenolic resin, and the derivative has a molecular structure as shown in Formula 3. , Formula 3, In Formula 3, R1 is H; the degree of polymerization n2 is 8.0 (average value calculated according to GPC). The equivalent weight of epoxy molecules in the epoxy derivative is 323.1 g / eq.

[0115] like Figure 2 As shown, a method for preparing epoxy derivatives includes: S1. Epichlorohydrin, a third catalyst, and cashew nut shell phenolic resin are subjected to a third catalytic reaction to obtain a third catalytic product; wherein, the temperature of the third catalytic reaction is 75℃ and the time of the third catalytic reaction is 1.5h; the mass m5 of the cashew nut shell phenolic resin and the mass m6 of the epichlorohydrin satisfy the following ratio: m5:m6=100:251; the mass m7 of the third catalyst and the mass m5 of the cashew nut shell phenolic resin satisfy the following ratio: m7:m5=67:100. S2. The third catalytic product is purified using a third solvent to obtain an epoxy derivative of cashew phenol-type dicyclopentadiene phenolic resin. The third catalyst is sodium hydroxide; when the third catalyst is sodium hydroxide, the sodium hydroxide exists in the form of an aqueous solution with a mass concentration of 30%.

[0116] The third solvent is toluene. The mass of the third solvent is 300:100 of the mass of the cashew phenol-type dicyclopentadiene phenolic resin.

[0117] In the third catalytic reaction, the temperature is first raised to 45°C for dissolution, then the third catalyst is added and stirred for 3 hours, and then the temperature is raised to the temperature required for the third catalytic reaction to carry out the third catalytic reaction.

[0118] Example 8 Compared to Example 2, the differences in this example are as follows, while the rest are the same: An epoxy derivative of a cashew phenol-type dicyclopentadiene phenolic resin, wherein the raw material for the epoxy derivative includes cashew phenol-type dicyclopentadiene phenolic resin, and the derivative has a molecular structure as shown in Formula 3, wherein the R1 group is H; and the degree of polymerization n2 is 10.1 (average value calculated according to GPC).

[0119] The mass m5 of the cashew phenol-type dicyclopentadiene phenolic resin and the mass m6 of epichlorohydrin satisfy the following ratio: m5:m6=100:220.2; the mass m7 of the third catalyst and the mass m5 of the cashew phenol-type dicyclopentadiene phenolic resin satisfy the following ratio: m7:m5=63.7:100.

[0120] The mass of the third solvent is 300:100 of the mass of the cashew phenol-type dicyclopentadiene phenolic resin.

[0121] Example 9 Compared to Example 3, the differences in this example are as follows, while the rest are the same: An epoxy derivative of a cashew phenol-type dicyclopentadiene phenolic resin, wherein the raw material for the epoxy derivative includes cashew phenol-type dicyclopentadiene phenolic resin, and the derivative has a molecular structure as shown in Formula 3, wherein the R1 group is H; and the degree of polymerization n2 is 12.8 (average value calculated according to GPC).

[0122] The mass m5 of the cashew phenol-type dicyclopentadiene phenolic resin and the mass m6 of the epichlorohydrin satisfy the following ratio: m5:m6=100:208.8; the mass m7 of the third catalyst and the mass m5 of the cashew phenol-type dicyclopentadiene phenolic resin satisfy the following ratio: m7:m5=62.7:100.

[0123] The mass of the third solvent is 350:100 of the mass of the cashew phenol-type dicyclopentadiene phenolic resin.

[0124] Example 10 Compared to Example 4, the differences in this example are as follows, while the rest are the same: An epoxy derivative of a cashew phenol-type dicyclopentadiene phenolic resin, wherein the raw material for the epoxy derivative includes cashew phenol-type dicyclopentadiene phenolic resin, and the derivative has a molecular structure as shown in Formula 3, wherein the R1 group is -CH3; and the degree of polymerization n2 is 8.28 (average value calculated according to GPC).

[0125] The mass m5 of the cashew phenol-type dicyclopentadiene phenolic resin and the mass m6 of epichlorohydrin satisfy the following ratio: m5:m6=100:182.6; the mass m7 of the third catalyst and the mass m5 of the cashew phenol-type dicyclopentadiene phenolic resin satisfy the following ratio: m7:m5=59.3:100.

[0126] The mass of the third solvent is 400:100 of the mass of the cashew phenol-type dicyclopentadiene phenolic resin.

[0127] Example 11 Compared to Example 7, the differences in this example are as follows, while the rest are the same: A composition for copper clad laminates, comprising, by mass parts, an active component and an active solvent (butanone); the active component comprises, by mass parts, 200 parts of an epoxy derivative, 30.6 parts of an active ester resin, 82.6 parts of a phosphorus-containing phenolic resin, and 2 parts of an imidazole catalyst; the active solvent comprises, by mass parts, 76.1 parts.

[0128] The active ester resin is DFE617 type active ester; the phosphorus-containing phenolic resin is DFE395 resin; the accelerator is diphenylimidazole; the composition also includes an active solvent for dissolving the active components, and the active solvent is butanone.

[0129] like Figure 3 As shown, a method for preparing a resin-clad copper board includes: S1. Impregnate the composition onto the surface of fiberglass cloth to obtain impregnated fiberglass cloth; S2. Dry the impregnated fiberglass cloth to obtain prepolymer fiberglass cloth; S3. Lay the multi-layer prepolymer fiberglass cloth together to obtain laminated fiberglass cloth; S4. Copper foil is adhered to both ends of the laminated fiberglass cloth and vacuum hot-pressed to obtain a resin-coated copper board.

[0130] Example 12 Compared to Example 7, the differences in this example are as follows, while the rest are the same: The composition comprises, by mass parts, an active component and an active solvent (butanone); the active component comprises 200 parts of an epoxy derivative, 32.4 parts of an active ester resin, 83.3 parts of a phosphorus-containing phenolic resin, and 2 parts of an imidazole catalyst; the active solvent comprises 76.6 parts by mass.

[0131] Example 13 Compared to Example 8, the differences in this example are as follows, while the rest are the same: The composition comprises, by mass parts, an active component and an active solvent (butanone); the active component comprises 200 parts of an epoxy derivative, 24.6 parts of an active ester resin, 84.6 parts of a phosphorus-containing phenolic resin, and 2 parts of an imidazole catalyst; the active solvent comprises 74.7 parts by mass.

[0132] Example 14 Compared to Example 8, the differences in this example are as follows, while the rest are the same: The composition comprises, by mass parts, an active component and an active solvent (butanone); the active component comprises 200 parts of an epoxy derivative, 27.2 parts of an active ester resin, 85.1 parts of a phosphorus-containing phenolic resin, and 2 parts of an imidazole catalyst; the active solvent comprises 74.8 parts by mass.

[0133] Example 15 Compared to Example 9, the differences in this example are as follows, while the rest are the same: The composition comprises, by mass parts, an active component and an active solvent (butanone); the active component comprises 200 parts of an epoxy derivative, 25.4 parts of an active ester resin, 83.7 parts of a phosphorus-containing phenolic resin, and 2.5 parts of an imidazole catalyst; the active solvent comprises 74.4 parts by mass.

[0134] Example 16 Compared to Example 9, the differences in this example are as follows, while the rest are the same: The composition comprises, by mass parts, an active component and an active solvent (butanone); the active component comprises, by mass parts, 200 parts of an epoxy derivative, 29.1 parts of an active ester resin, 85.5 parts of a phosphorus-containing phenolic resin, and 2.5 parts of an imidazole catalyst; the active solvent comprises, by mass parts, 75 parts.

[0135] Example 17 Compared to Example 10, the differences in this example are as follows, while the rest are the same: The composition comprises, by mass parts, an active component and an active solvent (butanone); the active component comprises 200 parts of an epoxy derivative, 23.6 parts of an active ester resin, 81.6 parts of a phosphorus-containing phenolic resin, and 3.0 parts of an imidazole catalyst; the active solvent comprises 73.6 parts by mass.

[0136] Example 18 Compared to Example 10, the differences in this example are as follows, while the rest are the same: The composition comprises, by mass parts, an active component and an active solvent (butanone); the active component comprises 200 parts of an epoxy derivative, 25.2 parts of an active ester resin, 83.7 parts of a phosphorus-containing phenolic resin, and 3.0 parts of an imidazole catalyst; the active solvent comprises 74.0 parts by mass.

[0137] Relevant experimental and effect data: 1. The molecular weight, hydroxyl equivalent, and softening point of the cashew phenol-type dicyclopentadiene phenolic resins obtained in Examples 1 to 6 were statistically analyzed, and the results are shown in Table 1.

[0138]

[0139] 2. The molecular weight, equivalent amount of epoxy molecules, and softening point of the epoxy derivatives of the cashew phenol type dicyclopentadiene phenolic resins obtained in Examples 7 to 10 were statistically analyzed, and the results are shown in Table 2.

[0140]

[0141] 3. The performance parameters of the copper-clad laminate compositions obtained in Examples 11 to 18 were statistically analyzed, and the results are shown in Table 3. In Table 3, (1) the dielectric constant was measured by using the plate method according to 2.5.5.9 of IPC-TM-650 at 10 GHz; (2) the dielectric loss factor tangent was measured by using the plate method according to 2.5.5.9 of IPC-TM-650 at 10 GHz; (3) the glass transition temperature (Tg) was measured by using the DSC method specified in 2.4.25 of IPC-TM-650 according to differential scanning calorimetry; (4) the thermal decomposition temperature (Td) was measured by using the method specified in 2.4.26 of IPC-TM-650; and (5) the thermal delamination time T300 was measured by using the method specified in 2.4.24 of IPC-TM-650. The method specified in .1 shall be used for determination; (6) Test method for immersion soldering time with copper foil: take a copper-clad board sample with a size of 100mm×100mm and copper foil on both sides, immerse it in 288℃ solder, and take the average value of the time when the copper-clad board sample does not delaminate and explode; (7) Test method for flame retardancy: refer to the UL94 test standard.

[0142]

[0143] As shown in Tables 1 to 3, the cashew phenol-type dicyclopentadiene phenolic resin provided in this application provides a high-performance electronic base resin with heat resistance, mechanical properties, and dielectric properties through a combination strategy of natural raw material substitution, integrated structural and functional design, synergistic realization of multiple properties, simple process, and wide application, under the premise of green environmental protection. This provides a new way for the sustainable development of electronic materials.

[0144] In summary, the cashew phenol-type dicyclopentadiene phenolic resin provided in this application embodiment is a high-performance electronic base resin prepared under green and environmentally friendly conditions through four dimensions: raw material selection, structural design, performance realization, and process.

[0145] In addition, the cashew nut shell phenolic resin provided in this application has a variety of rigid aromatic groups, which can ensure the heat resistance and excellent mechanical properties of the cashew nut shell phenolic resin. In addition, the main chain of the cashew nut shell phenolic resin contains flexible alkyl groups of cashew nut shell phenolic resin, which makes the cashew nut shell phenolic resin have self-toughening properties, and can obtain cashew nut shell phenolic resin with excellent impact resistance.

[0146] In addition, the embodiments of this application provide an epoxy derivative of a cashew nut phenol-type dicyclopentadiene phenolic resin, which contains the natural product cashew nut phenol. Cashew nut phenol is a natural green product-based resin, which meets the future market demand for greening, can realize the utilization of natural materials, and conforms to the green and environmentally friendly principle of high-performance materials. It is of great significance to the sustainable development and green development of high-performance materials in the future.

[0147] In addition, the embodiments of this application provide an epoxy derivative of a cashew phenol-type dicyclopentadiene phenolic resin. The main chain of this epoxy derivative is mainly composed of various aromatic groups (benzene ring, pentane ring, cyclohexane ring) and aliphatic chains, which can ensure that the mechanical structure of the epoxy derivative reduces the polarizability of the epoxy derivative to a certain extent and ensures the dielectric properties of the epoxy derivative.

[0148] Furthermore, the embodiments of this application provide a copper-clad laminate composition that has good dielectric properties and mechanical strength. Specifically, the copper-clad laminate composition has a dielectric constant of 3.68 to 3.78 at 10 GHz, a dielectric loss of 0.0069 to 0.0075, a glass transition temperature (DMA) of 178°C to 225°C, a thermal delamination time T300 > 60 min, and a copper-stretched solder resisting time > 300 s.

[0149] Furthermore, the embodiments of this application provide a method for preparing a composition for copper-clad laminates. This method is simple, widely applicable, and not limited to copper-clad laminates. It is also suitable for various other electronic components such as smart manufacturing and remote control equipment.

[0150] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed in this application.

Claims

1. A cardanol-type dicyclopentadiene phenol-type resin, characterized by, The cashew phenol type dicyclopentadiene phenol type resin has a molecular structure as shown in Formula 1, Formula 1, In Formula 1, the R1group is at least one of H, -CH3, -CH2CH3, and n1 is a polymerization degree of 0 to 13.

2. The cardanol-based dicyclopentadiene phenol-based resin according to claim 1, characterized by, An equivalent of the hydroxyl group in the cardanol type dicyclopentadiene phenolic resin is 256 g / eq to 330 g / eq.

3. A method for producing the cardanol-type dicyclopentadiene phenol-type resin described in claim 1 or 2, characterized by, The method comprises: carrying out a first catalytic reaction on dicyclopentadiene, cardanol and a first catalyst to obtain a first reaction product; carrying out a first purification treatment on the first reaction product using a first solvent to obtain a cardanol intermediate; wherein the cardanol intermediate has a molecular structure as shown in formula 2, formula 2; carrying out a second catalytic reaction on a monophenol compound, a second catalyst and the cardanol intermediate to obtain a second reaction product; carrying out a second purification on the second reaction product using small materials and a second solvent to obtain a cardanol type dicyclopentadiene phenolic resin.

4. The method of claim 3, wherein, The amount of substance n1 of the dicyclopentadiene and the amount of substance n2 of the cardanol satisfy: n1:n2=1:(0.25 to 1.00); and / or The amount of substance of the first catalyst is 0.01% to 0.07% of the amount of substance of the cardanol; and / or The mass m1 of the cardanol intermediate and the mass m2 of the monophenol compound satisfy: m1:m2=100:(80 to 150); and / or The mass m3 of the second catalyst and the mass m1 of the cardanol intermediate satisfy: m3:m1=(0.40 to 1.80):100; and / or The mass m4 of the small materials and the mass m1 of the cardanol intermediate satisfy: m4:m1=(0.14 to 0.80):

100.

5. The method of claim 3, wherein, The category of the first catalyst includes at least one of boron trifluoride ether, triflic acid, anhydrous aluminum chloride, p-toluene sulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid and phosphoric acid; and / or The category of the first solvent includes at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone and ethyl acetate; and / or The category of the monophenol compound includes at least one of phenol, p-cresol, p-ethyl phenol, p-octyl phenol and p-tetraoctyl phenol; and / or The category of the second catalyst includes at least one of methyl sulfonic acid, boron trifluoride ether, boron trifluoride methanol, dimethyl sulfonic acid, hydrochloric acid, p-toluene sulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid and phosphoric acid; and / or The category of the small materials includes at least one of sodium bicarbonate, sodium carbonate, sodium phosphate, potassium carbonate, magnesium oxide, calcium oxide, calcium hydroxide, magnesium carbonate; and / or The category of the second solvent includes at least one of chloroform, toluene, xylene, methyl isobutyl ketone, butanone and ethyl acetate.

6. The method of claim 3, wherein, The temperature of the first catalytic reaction is 55°C to 90°C, and the time of the first catalytic reaction is 5h to 36h; and / or The temperature of the second catalytic reaction is 90°C to 120°C, and the time of the second catalytic reaction is 3h to 8h.

7. An epoxy derivative of a cardanol-type dicyclopentadiene phenolic resin, characterized in that, The raw material of the epoxy derivative includes the cashew phenol type dicyclopentadiene phenol type resin according to claim 1 or 2, and the derivative has a molecular structure as shown in formula 3, Formula 3, In Formula 3, the R1group is at least one of H, -CH3, -CH2CH3, and n2 is a polymerization degree of 0 to 21. An equivalent of the epoxy molecule in the epoxy derivative is 297 g / eq to 366 g / eq.

8. A method of preparing the epoxy derivative of claim 7, characterized in that, The method comprises: Epichlorohydrin, a third catalyst, and the cashew nut shell phenolic resin according to claim 1 or 2 are subjected to a third catalytic reaction to obtain a third catalytic product; wherein the temperature of the third catalytic reaction is 60°C to 90°C, and the time of the third catalytic reaction is 1 h to 5 h; the mass m5 of the cashew nut shell phenolic resin and the mass m6 of the epichlorohydrin satisfy the following ratio: m5:m6 = 100:(180 to 340); the mass m7 of the third catalyst and the mass m5 of the cashew nut shell phenolic resin satisfy the following ratio: m7:m5 = (59.0 to 67.7):100; The third catalytic product was purified using a third solvent to obtain an epoxy derivative of cashew phenol-type dicyclopentadiene phenolic resin. The third catalyst includes at least one of triethylamine, ammonia, sodium silicate, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; and / or The third solvent includes at least one of toluene, xylene, methyl isobutyl ketone, and ethyl acetate.

9. A composition for a copper clad laminate, characterized by comprising: The composition comprises, by weight parts, an active component and an active solvent; the active component comprises, by weight parts, the epoxy derivative of claim 7: 150 to 200 parts, an active ester resin: 20 to 50 parts, a phosphorus-containing phenolic resin: 80 to 95 parts, and an imidazole catalyst: 2 to 5 parts; the active solvent comprises, by weight parts, 55 to 75 parts.

10. A method for preparing a resin-coated copper board, characterized in that, The preparation method includes: The composition of claim 9 is impregnated onto the surface of a fiberglass cloth to obtain an impregnated fiberglass cloth. The impregnated fiberglass cloth is dried to obtain prepolymer fiberglass cloth; The multilayer prepolymer fiberglass cloth is stacked to obtain a laminated fiberglass cloth; Copper foil is adhered to both ends of the laminated fiberglass cloth and then vacuum hot-pressed to obtain a resin-coated copper plate.

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