Dicyclopentadiene phenol resin and preparation method thereof, dicyclopentadiene phenol epoxy resin and preparation method and application thereof

Abstract

The invention provides dicyclopentadiene phenol resin and a preparation method thereof, dicyclopentadiene phenol epoxy resin and a preparation method and application thereof. Compared with common dicyclopentadiene phenol resin, the dicyclopentadiene phenol resin has unsaturated cycloolefin active functional groups at the tail ends of molecular chains, so that the reactivity of the resin can be improved, and the application field of the dicyclopentadiene phenol resin is expanded.

Description

Technical Field

[0001] This invention relates to the field of synthetic resin technology, and in particular to a dicyclopentadiene phenol resin and its preparation method, a dicyclopentadiene phenol epoxy resin and its preparation method and applications. Background Technology

[0002] Dicyclopentadiene phenol resin is an important raw material for semiconductor sealing materials and can also be used in the production of rubber antioxidants, epoxy resin modifiers, printing ink carriers, adhesives, laminates, and powder coatings. Dicyclopentadiene phenol epoxy resin is a type of epoxy resin with a special skeletal structure. Compared to general-purpose bisphenol A epoxy resin, its molecular structure contains not only benzene rings but also a dicyclopentadiene alicyclic structure. This type of epoxy resin exhibits excellent heat resistance, low moisture absorption, low elastomerism, and high adhesion and sealing properties. It can not only replace o-cresyl formaldehyde epoxy resin to improve the heat resistance, water absorption, and crack resistance of semiconductor packages, but also has excellent moisture resistance and saltwater corrosion resistance, making it suitable as a primer in furniture, electrical appliances, and shipbuilding.

[0003] Currently, both dicyclopentadiene phenol resin and dicyclopentadiene phenol epoxy resin are linear resins with phenol structures at both ends. In this type of resin structure, the active double bonds of dicyclopentadiene have undergone addition reactions, and the active sites of the resin are all on the phenol units. Therefore, the reactivity of the resin is limited.

[0004] CN104193592A discloses a dicyclopentadienol-type resin, which synthesizes a dicyclopentadienol-type resin with phenol units at both ends through phenol and dicyclopentadiene, with a dimer content of more than 80 wt% and a softening point of less than 85°C; and obtains a dicyclopentadienol-type epoxy resin by reacting the above-obtained resin with epichlorohydrin under the action of a catalyst, with a dimer content of more than 70 wt% and a softening point of less than 60°C.

[0005] CN111647134A discloses a method for synthesizing dicyclopentadiene phenol epoxy resin. The method involves a stepwise synthesis process, with corresponding catalysts added according to the reaction requirements of different processes to ensure the reaction proceeds fully, thereby improving the product yield and the quality and purity of the product. At the same time, a reduction decolorization process is used to reduce the color of the product, ultimately yielding a dicyclopentadiene phenol epoxy resin with low color, high softening point, high epoxy value, and low content of organic and inorganic chlorines.

[0006] CN106542970A discloses a dicyclopentadienol type resin. By comprehensively improving the preparation and recycling steps of DCPD phenol type resin, a simple, practical, environmentally friendly method is obtained that can simultaneously reduce costs and energy consumption, is suitable for industrial applications, and can simultaneously obtain high-quality products for recycling. This method also reduces the amount of raw materials and wastewater generated during the synthesis process of dicyclopentadienol type resin.

[0007] Therefore, synthesizing dicyclopentadiene phenol resins containing active unsaturated cyclic olefin end groups is a technical problem that urgently needs to be solved in this field. The structure contains active unsaturated cyclic olefin functional groups at both ends, which can increase the reactivity of the resin and expand its application prospects. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a dicyclopentadiene phenol resin and its preparation method, a dicyclopentadiene phenol epoxy resin and its preparation method, and its applications. The dicyclopentadiene phenol resin and the dicyclopentadiene phenol epoxy resin have unsaturated cyclic olefin structures at both ends of their molecular chains, which increases the reactivity of the resin, improves the crosslinking density and curing efficiency of the resin system, thereby enhancing the overall performance of the resin and expanding its potential application areas.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a dicyclopentadiene phenol resin having the structure shown in Formula I or Formula II:

[0011]

[0012] R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, phenyl, substituted phenyl, or C1-C10 alkyl, and at least two of R1, R3, and R5 are hydrogen.

[0013] n is an integer from 0 to 10, and m is 0 or 1.

[0014] The dicyclopentadiene phenol resin provided by this invention increases the reactivity of the resin by introducing unsaturated cyclic olefin structures at both ends of the molecular chain, thereby improving the crosslinking density and curing efficiency of the resin system and enhancing the overall performance of the resin. This solves the problem of limited reactivity of traditional dicyclopentadiene phenol resin.

[0015] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0016] Preferably, the substituent in the substituted phenyl group is a halogen, phenyl, substituted phenyl, or a C1-C10 alkyl group.

[0017] In a second aspect, the present invention provides a method for preparing the dicyclopentadiene phenol resin as described in the first aspect, the method comprising the following steps:

[0018] Dicyclopentadiene and phenol are reacted to obtain the dicyclopentadiene-phenol resin.

[0019] Preferably, the molar ratio of dicyclopentadiene to phenol is 1:(0.1-1), for example, it can be 1:0.2, 1:0.4, 1:0.6 or 1:0.8, and more preferably 1:(0.5-1).

[0020] Preferably, the reaction is carried out in the presence of a catalyst.

[0021] Preferably, the catalyst comprises any one or a combination of at least two of p-toluenesulfonic acid, aluminum trichloride, or boron trifluoride ethyl ether, and more preferably boron trifluoride ethyl ether.

[0022] Preferably, the mass of the catalyst is 0.05-3.0% of the mass of dicyclopentadiene, for example, it can be 0.06%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0% or 2.5%, and more preferably 1.0-2.0%.

[0023] Preferably, the reaction temperature is 80-130°C, for example, 90°C, 100°C, 110°C or 120°C, and more preferably 100-110°C.

[0024] Preferably, the reaction time is 1-4 hours, for example, 2 hours or 3 hours, and more preferably 2-3 hours.

[0025] Preferably, phenol is added dropwise after the dicyclopentadiene is added to the reaction vessel.

[0026] Preferably, the temperature at which the phenol is added is 60-100°C, for example, 70°C, 80°C or 90°C, and more preferably 70-90°C.

[0027] Preferably, the phenol is added to the reaction system within 1-3 hours, for example, 1.5 hours, 2 hours, or 2.5 hours, and more preferably 1-2 hours.

[0028] Preferably, the reaction further includes a post-processing step.

[0029] Preferably, the post-processing includes dilution, washing with water, separation, and solvent removal.

[0030] Preferably, the diluent includes any one or a combination of at least two of toluene, xylene, or methyl isobutyl ketone, and more preferably toluene.

[0031] Preferably, the solvent removal is performed under vacuum conditions.

[0032] Preferably, the vacuum degree is -0.1 to -0.05 MPa, for example, it can be -0.09 MPa, -0.08 MPa, -0.07 MPa or -0.06 MPa, and more preferably -0.09 to -0.07 MPa.

[0033] Preferably, the solvent removal is carried out at 130-150°C, for example, 135°C, 140°C or 145°C, and more preferably 130-140°C.

[0034] Preferably, the preparation method specifically includes the following steps:

[0035] Dicyclopentadiene is added to the reaction vessel and heated to 60-100℃. Phenol is added to the reaction system within 1-3 hours. Under the action of a catalyst, the reaction is carried out at 80-130℃ for 1-4 hours.

[0036] After the reaction is complete, solvent is added for dilution, followed by washing with water, separation, and removal of solvent under conditions of -0.1 to -0.05 MPa and 130-150 °C to obtain the dicyclopentadiene phenol resin.

[0037] The molar ratio of dicyclopentadiene to phenol is 1:(0.1-1);

[0038] The catalyst comprises any one or a combination of at least two of p-toluenesulfonic acid, aluminum trichloride, or boron trifluoride ether.

[0039] Thirdly, the present invention provides a dicyclopentadiene phenol epoxy resin having the structure shown in Formula III or Formula IV:

[0040]

[0041] R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, phenyl, substituted phenyl, or C1-C10 alkyl, and at least two of R1, R3, and R5 are hydrogen.

[0042] n is an integer from 0 to 10, and m is 0 or 1;

[0043] The substituents in the substituted phenyl group are halogens, phenyl groups, substituted phenyl groups, or C1-C10 alkyl groups.

[0044] The dicyclopentadiene phenol epoxy resin provided by this invention increases the reactivity of the resin by introducing unsaturated cycloolefin structures at both ends of the molecular chain, thereby improving the crosslinking density and curing efficiency of the resin system and enhancing the overall performance of the resin. This solves the problem of limited reactivity of traditional dicyclopentadiene phenol epoxy resin.

[0045] Fourthly, the present invention provides a method for preparing the dicyclopentadiene phenol epoxy resin as described in the third aspect, the method comprising the following steps:

[0046] Epichlorohydrin is reacted with the dicyclopentadiene phenol resin according to claim 1 to obtain the dicyclopentadiene phenol epoxy resin.

[0047] Preferably, the mass ratio of epichlorohydrin to dicyclopentadiene phenol resin is (1-5):1; for example, it can be 2:1, 3:1 or 4:1, and more preferably (2-4):1.

[0048] Preferably, the reaction is carried out under reflux conditions.

[0049] Preferably, the reflux temperature is 50-100℃, for example, it can be 60℃, 70℃, 80℃ or 90℃, and more preferably 60-80℃.

[0050] Preferably, the reaction is carried out under alkaline conditions.

[0051] Preferably, the alkaline substance includes sodium hydroxide solution and / or potassium hydroxide solution.

[0052] Preferably, the concentration of the alkaline substance is 25%-48%, for example, it can be 30%, 35%, 40% or 45%, etc.

[0053] Preferably, the alkaline substance is added over a period of 2-5 hours, such as 2.5 hours, 3 hours, 3.5 hours, 4 hours or 4.5 hours, and more preferably 3-4 hours.

[0054] Preferably, the reaction further includes a post-processing step.

[0055] Preferably, the post-processing includes dilution, washing with water, separation, and solvent removal.

[0056] Preferably, the diluent includes any one or a combination of at least two of toluene, xylene, and methyl isobutyl ketone, and more preferably toluene.

[0057] Preferably, the solvent removal is performed under vacuum conditions.

[0058] Preferably, the vacuum degree is -0.1 to -0.05 MPa, for example, it can be -0.09 MPa, -0.08 MPa, -0.07 MPa or -0.06 MPa, and more preferably -0.09 to -0.07 MPa.

[0059] Preferably, the solvent removal is carried out at 110-150°C, for example, 120°C, 130°C or 140°C, and more preferably 120-140°C.

[0060] Preferably, the preparation method specifically includes the following steps:

[0061] Epichlorohydrin and dicyclopentadiene phenol resin were placed in a reaction vessel. After the reactants dissolved, an alkaline substance was added dropwise to the reaction system over 2-5 hours. The mixture was refluxed at 50-100°C until the alkaline substance was completely added and the reaction was complete.

[0062] The resin was diluted with solvent, washed with water, separated, and the solvent was removed under conditions of -0.1 to -0.05 MPa and 110-150°C to obtain the dicyclopentadiene phenol epoxy resin.

[0063] The mass ratio of epichlorohydrin to dicyclopentadiene phenol resin is (1-5):1.

[0064] Fifthly, the present invention provides the application of the dicyclopentadiene phenol resin as described in the first aspect or the dicyclopentadiene phenol epoxy resin as described in the third aspect in copper clad laminates, semiconductor packaging, coatings, adhesives or composite materials.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] The dicyclopentadiene phenol resin and dicyclopentadiene phenol epoxy resin provided by this invention have active unsaturated cyclic olefin structures at the molecular chain ends. Compared with ordinary dicyclopentadiene phenol resin, the active unsaturated cyclic olefin functional groups at the molecular chain ends are increased, which can expand the application fields of dicyclopentadiene phenol resin and dicyclopentadiene phenol epoxy resin. Attached Figure Description

[0067] Figure 1 The infrared spectra of the dicyclopentadiene phenol resin and the dicyclopentadiene phenol epoxy resin prepared in Example 1 are shown.

[0068] Figure 2 The dicyclopentadiene phenol resin prepared in Example 1 1 H NMR spectrum;

[0069] Figure 3 The dicyclopentadiene phenol epoxy resin prepared in Example 1 1HNMR spectrum;

[0070] Figure 4 The dicyclopentadiene phenol resin prepared in Comparative Example 1 1 H NMR spectrum;

[0071] Figure 5 The dicyclopentadiene phenol epoxy resin prepared in Comparative Example 1 1 HNMR spectrum. Detailed Implementation

[0072] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0073] Example 1

[0074] (1) Add 200.0 g of dicyclopentadiene (1.52 mol) to a 1000 mL round-bottom flask equipped with a stirrer, temperature control and a feeding funnel, heat to 80 °C, then add 1.4 g of boron trifluoride ether (0.01 mol), weigh 94.0 g of phenol (1.0 mol), add it dropwise to the reaction system through the feeding funnel over 1.5 h, react at 100 °C for 1.5 h, then add 300 mL of toluene, stir, wash with water, separate the liquids, and heat under reduced pressure to 135.0 °C to obtain dicyclopentadiene phenol resin.

[0075] (2) Add 100.0g of dicyclopentadiene phenol resin to a four-necked flask containing 160.0g of epichlorohydrin, heat to 70℃, stir to dissolve, and after complete dissolution, weigh 32.5g of 48% NaOH solution and slowly add it dropwise to the four-necked flask through a constant pressure funnel. Reduce pressure and reflux at 70℃, adding the solution over 2 hours. Stop the reaction after the alkali solution has been added. Then add 300mL of toluene, stir, wash with water, separate the contents, and heat to 140.0℃ under reduced pressure to obtain dicyclopentadiene phenol epoxy resin.

[0076] Infrared spectroscopy was performed on dicyclopentadiene phenol resin and dicyclopentadiene phenol epoxy resin, and the results are as follows: Figure 1 As shown: In the infrared spectrum of dicyclopentadiene phenol resin, 3423 cm⁻¹ -1 A broad absorption peak is observed at 3423 cm⁻¹, which is a characteristic peak of the phenolic hydroxyl group; in the infrared spectrum of dicyclopentadiene phenol epoxy resin, the peak is at 3423 cm⁻¹. -1 The characteristic peak of the phenolic hydroxyl group disappears at 1291 cm⁻¹. -1 and 917cm -1 Characteristic peaks of epoxy groups appear at the location.

[0077] The 1H NMR spectrum of dicyclopentadiene phenol resin was analyzed using Bruker Ascend III 400M with deuterated dimethyl sulfoxide as the solvent. The results are as follows: Figure 2 As shown: the chemical shifts of the phenolic hydroxyl group are between 8.9 ppm and 9.3 ppm; the chemical shifts of the hydrogen atoms in the cyclopentene double bond are 5.5 ppm and 5.7 ppm.

[0078] The 1H NMR spectrum of dicyclopentadiene phenol epoxy resin was analyzed using Bruker Ascend III 400M with deuterated dimethyl sulfoxide as the solvent. The results are as follows: Figure 3 As shown: the chemical shift of the phenolic hydroxyl group disappears between 8.9 ppm and 9.3 ppm, and the chemical shift of the epoxy group appears at 3.9 ppm and 4.3 ppm, indicating that the phenolic hydroxyl group has completely reacted and generated new epoxy groups; at the same time, 5.5 ppm and 5.7 ppm are hydrogens of the cyclopentene double bond, indicating that the cycloolefin structure is retained in the dicyclopentadiene phenol epoxy resin.

[0079] Example 2

[0080] (1) Add 158.0 g of dicyclopentadiene (1.20 mol) to a 1000 mL round-bottom flask equipped with a stirrer, temperature control and a feeding funnel, heat to 80 °C, then add 1.3 g of boron trifluoride ether (0.0092 mol), weigh 91.0 g of phenol (0.97 mol), add it dropwise to the reaction system through the feeding funnel over 2 h, react at 105 °C for 2.5 h, then add 300 mL of toluene, stir, wash with water, separate the liquid, and heat under reduced pressure to 140.0 °C to obtain dicyclopentadiene phenol resin.

[0081] (2) Add 90.0g of dicyclopentadiene phenol resin to a four-necked flask containing 160.0g of epichlorohydrin, heat to 80℃, stir to dissolve, and after complete dissolution, weigh 30.7g of 46% NaOH solution and slowly add it dropwise to the four-necked flask through a constant pressure funnel. Reduce pressure, reflux at 70℃, and add the solution over 2.5h. Stop the reaction after the alkali solution has been added. Then add 300mL of toluene, stir, wash with water, separate the contents, and heat to 145.0℃ under reduced pressure to obtain dicyclopentadiene phenol epoxy resin.

[0082] Example 3

[0083] (1) Add 150.0 g of dicyclopentadiene (1.14 mol) to a 1000 mL round-bottom flask equipped with a stirrer, temperature control and a feeding funnel, heat to 80 °C, then add 1.5 g of boron trifluoride ether (0.0105 mol), weigh 100.0 g of phenol (1.06 mol), and add it dropwise to the reaction system through the feeding funnel over 2.5 h. React at 110 °C for 1.5 h, then add 300 mL of toluene, stir, wash with water, separate the liquids, and heat under reduced pressure to 145.0 °C to obtain dicyclopentadiene phenol resin.

[0084] (2) Add 150.0g of dicyclopentadiene phenol resin to a four-necked flask containing 250.0g of epichlorohydrin, heat to 80℃, stir to dissolve, and after complete dissolution, weigh 60.5g of 45% NaOH solution and slowly add it dropwise to the four-necked flask through a constant pressure funnel. Reduce pressure, reflux at 70℃, and add the solution within 2 hours. Stop the reaction after the alkali solution has been added. Then add 300mL of toluene, stir, wash with water, separate the contents, and heat to 140.0℃ under reduced pressure to obtain dicyclopentadiene phenol epoxy resin.

[0085] Comparative Example 1

[0086] (1) Add 188.0 g of phenol (2.0 mol) to a 1000 mL round-bottom flask equipped with a stirrer, temperature control and a feeding funnel, heat to 80 °C, then add 2.0 g of boron trifluoride ether (0.014 mol), weigh 132.0 g of dicyclopentadiene (1.0 mol), add it dropwise to the reaction system through the feeding funnel over 1.5 h, react at 100 °C for 1.5 h, then add 300 mL of toluene, stir, wash with water, separate the liquids, and heat under reduced pressure to 135.0 °C to obtain dicyclopentadiene phenol resin.

[0087] (2) Add 100.0g of dicyclopentadiene phenol resin to a four-necked flask containing 250.0g of epichlorohydrin, heat to 70℃, stir to dissolve, and after complete dissolution, weigh 32.5g of 48% NaOH solution and slowly add it dropwise to the four-necked flask through a constant pressure funnel. Reduce pressure and reflux at 70℃, adding the solution over 2 hours. Stop the reaction after the alkali solution has been added. Then add 300mL of toluene, stir, wash with water, separate the contents, and heat to 140.0℃ under reduced pressure to obtain dicyclopentadiene phenol epoxy resin.

[0088] The 1H NMR spectrum of dicyclopentadiene phenol resin was analyzed using Bruker Ascend III 400M with deuterated dimethyl sulfoxide as the solvent. The results are as follows: Figure 4 As shown: 9.2 ppm is the chemical shift of the phenolic hydroxyl group; there is no peak at 5 ppm-6 ppm, indicating that the molecular structure does not contain a terminal cyclic olefin structure.

[0089] The 1H NMR spectrum of dicyclopentadiene phenol epoxy resin was analyzed using Bruker Ascend III 400M with deuterated dimethyl sulfoxide as the solvent. The results are as follows: Figure 5 As shown: the chemical shift of the phenolic hydroxyl group disappears at 9.2 ppm, and the chemical shift of the epoxy group appears at 3.9 ppm and 4.3 ppm; indicating that the phenolic hydroxyl group has completely reacted to generate a new epoxy group. There is no peak at 5 ppm-6 ppm, indicating that the molecular structure does not contain a terminal unsaturated cyclic olefin structure.

[0090] Performance testing

[0091] (1) Softening point: Tested in accordance with GBT12007.6-1989.

[0092] (2) Epoxy equivalent: Tested in accordance with GB / T 4612-2008.

[0093] (3) Infrared spectrum: Tested in accordance with GB / T 21186-2007.

[0094] (4) Molecular weight: Waters GPC at room temperature was used in the United States. The mobile phase was tetrahydrofuran (THF), the standard was polystyrene (PS), and the test temperature was 35℃.

[0095] The performance of the dicyclopentadiene phenol resin and dicyclopentadiene phenol epoxy resin provided in the above embodiments and comparative examples was tested, and the results are shown in Table 1:

[0096] Table 1

[0097]

[0098] As shown in Table 1, the dicyclopentadiene phenol resin and dicyclopentadiene phenol epoxy resin provided by the present invention have a low softening point (43.0-58.0℃), and the dicyclopentadiene phenol epoxy resin has a high epoxy equivalent.

[0099] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A dicyclopentadiene phenol resin, characterized in that, The dicyclopentadiene phenol resin has the structure shown in Formula I or Formula II: R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, phenyl, substituted phenyl, or C1-C10 alkyl, and at least two of R1, R3, and R5 are hydrogen. n is an integer from 0 to 10, and m is 0 or 1.

2. The dicyclopentadiene phenol resin according to claim 1, characterized in that, The substituents in the substituted phenyl group are halogens, phenyl groups, substituted phenyl groups, or C1-C10 alkyl groups.

3. The method for preparing dicyclopentadiene phenol resin according to claim 1 or 2, characterized in that, The preparation method includes the following steps: Dicyclopentadiene and phenol are reacted to obtain the dicyclopentadiene-phenol resin.

4. The preparation method according to claim 3, characterized in that, The molar ratio of dicyclopentadiene to phenol is 1:(0.1-1); preferably 1:(0.5-1). Preferably, the reaction is carried out in the presence of a catalyst; Preferably, the catalyst comprises any one or a combination of at least two of p-toluenesulfonic acid, aluminum trichloride, or boron trifluoride diethyl ether, and more preferably boron trifluoride diethyl ether; Preferably, the mass of the catalyst is 0.05-3.0% of the mass of dicyclopentadiene, more preferably 1.0-2.0%; Preferably, the reaction temperature is 80-130°C, more preferably 100-110°C; Preferably, the reaction time is 1-4 hours, more preferably 2-3 hours; Preferably, phenol is added dropwise after the dicyclopentadiene is added to the reaction vessel; Preferably, the temperature at which the phenol is added is 60-100°C, more preferably 70-90°C; Preferably, the phenol is added to the reaction system within 1-3 hours, more preferably within 1-2 hours; Preferably, the reaction further includes a post-processing step; Preferably, the post-processing includes dilution, washing with water, separation, and solvent removal; Preferably, the diluent includes any one or a combination of at least two of toluene, xylene, or methyl isobutyl ketone, and more preferably toluene; Preferably, the solvent removal is performed under vacuum conditions; Preferably, the vacuum degree is -0.1 to -0.05 MPa, more preferably -0.09 to -0.07 MPa; Preferably, the solvent removal is carried out at 130-150°C, and more preferably at 130-140°C.

5. The preparation method according to claim 3 or 4, characterized in that, The preparation method specifically includes the following steps: Dicyclopentadiene is added to the reaction vessel and heated to 60-100℃. Phenol is added to the reaction system within 1-3 hours. Under the action of a catalyst, the reaction is carried out at 80-130℃ for 1-4 hours. After the reaction is complete, solvent is added for dilution, followed by washing with water, separation, and removal of solvent under conditions of -0.1 to -0.05 MPa and 130-150 °C to obtain the dicyclopentadiene phenol resin. The molar ratio of dicyclopentadiene to phenol is 1:(0.1-1); The catalyst comprises any one or a combination of at least two of p-toluenesulfonic acid, aluminum trichloride, or boron trifluoride ether.

6. A dicyclopentadiene phenol epoxy resin, characterized in that, The dicyclopentadiene phenol epoxy resin has the structure shown in Formula III or Formula IV: R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, phenyl, substituted phenyl, or C1-C10 alkyl, and at least two of R1, R3, and R5 are hydrogen. n is an integer from 0 to 10, and m is 0 or 1; The substituents in the substituted phenyl group are halogens, phenyl groups, substituted phenyl groups, or C1-C10 alkyl groups.

7. The method for preparing dicyclopentadiene phenol epoxy resin according to claim 6, characterized in that, The preparation method includes the following steps: Epichlorohydrin is reacted with the dicyclopentadiene phenol resin according to claim 1 to obtain the dicyclopentadiene phenol epoxy resin.

8. The preparation method according to claim 7, characterized in that, The mass ratio of epichlorohydrin to dicyclopentadiene phenol resin is (1-5):1; preferably (2.0-4.0):

1. Preferably, the reaction is carried out under reflux conditions; Preferably, the reflux temperature is 50-100°C, more preferably 60-80°C; Preferably, the reaction is carried out under alkaline conditions; Preferably, the alkaline substance includes sodium hydroxide solution and / or potassium hydroxide solution; Preferably, the concentration of the alkaline substance is 25%-48%; Preferably, the alkaline substance is added over a period of 2-5 hours, more preferably 3-4 hours. Preferably, the reaction further includes a post-processing step; Preferably, the post-processing includes dilution, washing with water, separation, and solvent removal; Preferably, the diluent includes any one or a combination of at least two of toluene, xylene, or methyl isobutyl ketone, and more preferably toluene; Preferably, the solvent removal is performed under vacuum conditions; Preferably, the vacuum degree is -0.1 to -0.05 MPa, more preferably -0.09 to -0.07 MPa; Preferably, the solvent removal is carried out at 110-150°C, and more preferably at 120-140°C.

9. The preparation method according to claim 7 or 8, characterized in that, The preparation method specifically includes the following steps: Epichlorohydrin and dicyclopentadiene phenol resin were placed in a reaction vessel. After the reactants dissolved, an alkaline substance was added dropwise to the reaction system over 2-5 hours. The mixture was refluxed at 50-100°C until the alkaline substance was completely added and the reaction was complete. The resin was diluted with solvent, washed with water, separated, and the solvent was removed under conditions of -0.1 to -0.05 MPa and 110-150°C to obtain the dicyclopentadiene phenol epoxy resin. The mass ratio of epichlorohydrin to dicyclopentadiene phenol resin is (1-5):

1.

10. The use of a dicyclopentadiene phenol resin as described in claim 1 or 2, or a dicyclopentadiene phenol epoxy resin as described in claim 6, in copper clad laminates, semiconductor packaging, coatings, adhesives, or composite materials.

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