A composition of polyolefin-containing DCPD epoxy resin and copper-clad laminate, and its preparation method.

Abstract

This invention discloses a polyolefin-containing DCPD epoxy resin and a copper-clad laminate composition thereof, and its preparation method. The method is characterized by: polymerizing polyallyl phenol and catalyst A at high temperature to form polyallyl phenol; then reacting DCPD, polyallyl phenol, and catalyst B at high temperature to form a polyolefin-containing DCPD phenol resin; subsequently, epoxidizing the resin with epichlorohydrin and alkaline catalyst C to synthesize a polyolefin-containing DCPD epoxy resin; finally, mixing the resin with maleimide resin, phosphorus-containing phenolic resin, imidazole accelerator, inorganic filler, and solvent to obtain the polyolefin-containing DCPD epoxy resin composition for copper-clad laminates. The polyolefin-containing DCPD epoxy resin and copper-clad laminate composition prepared by this invention exhibits low dielectric constant, low dielectric loss, and high heat resistance, making it particularly suitable as a raw material for copper-clad laminates and highly practical.

Description

Technical Field

[0001] This invention pertains to organic compounds, compositions for copper-clad laminates, and their preparation, specifically relating to a polyolefin-containing DCPD (DCPD is short for dicyclopentadiene) epoxy resin and a composition for copper-clad laminates, as well as a method for its preparation. The polyolefin-containing DCPD epoxy resin and the composition for copper-clad laminates of this invention possess characteristics such as low dielectric constant, low dielectric loss, and high heat resistance, making them particularly suitable as raw materials for copper-clad laminates. Background Technology

[0002] Currently, with the emergence of cutting-edge technologies such as 5G, artificial intelligence, big data, and blockchain, my country's copper clad laminate (CCL) industry has also experienced rapid development. The technological level of CCL is gradually shifting from low-end to high-end, with high frequency and high speed becoming the mainstream research and development direction. Traditional resins, such as bisphenol A epoxy and phenolic resins, can no longer meet the requirements of high frequency and high speed, demanding higher information transmission rates, lower information loss, and higher heat resistance.

[0003] In the existing technology, bismaleimide resin, polyphenylene ether resin, cyanate ester resin, low dielectric benzoxazine resin, hydrocarbon resin, low dielectric epoxy resin, etc., have excellent dielectric properties and heat resistance due to the presence of high heat resistance and low polarity groups in their structure, as well as good structural symmetry or large molecular free volume. They have become the new main substrates for high frequency and high speed copper clad laminates. Among low-dielectric epoxy resins, DCPD epoxy resins, due to the introduction of a dicyclopentadiene ring (DCPD) with extremely low polarity into their structure, result in epoxy resins and products with good dielectric properties, making them favored by the copper clad laminate industry. Examples include: Chinese invention patent application publications CN106893258A ("An epoxy resin composition and a prepreg containing it, a laminate and a printed circuit board"), CN108047648A ("A resin composition suitable for high-speed, high-reliability copper clad laminate and its preparation method"), CN105368001A ("A halogen-free epoxy resin composition and its preparation method and its application"), CN102127291A ("A halogen-free epoxy resin composition and a cover film prepared therefrom"), and CN105415778A ("A halogen-free high-frequency, high-speed copper clad laminate and its preparation method"). The DCPD epoxy mentioned in these reports is basically prepared by reacting dicyclopentadiene with phenol or alkylphenol to synthesize DCPD phenolic resin, followed by epoxidation of the phenolic hydroxyl groups. The dielectric constant (Dk) of this type of resin casting is 3.0–3.5, the dielectric loss (Df) is 0.010–0.020, and the glass transition temperature (Tg) is 140–160℃. Such performance is insufficient to meet the increasingly stringent dielectric performance targets (Df≤0.004, Tg≥200℃) of high-frequency, high-speed copper-clad laminates for 5G communication, thus limiting its further application. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a composition for DCPD epoxy resin and copper-clad laminate containing polyolefins, and a method for preparing the same. This provides a composition for DCPD epoxy resin and copper-clad laminate containing polyolefins, and a method for preparing the same, characterized by low dielectric constant, low dielectric loss, and high heat resistance.

[0005] The present invention is: a DCPD epoxy resin containing polyolefin, characterized in that: the chemical structure of the epoxy resin simultaneously contains a dicyclopentadiene ring, an epoxy ring and a polyolefin structure, and its chemical structural formula is shown in (1) to (3).

[0006] In equations (1) to (3): m is 0 to 10, and n is 30 to 80.

[0007] Another aspect of this invention is a method for preparing a polyolefin-containing DCPD epoxy resin, characterized by the following steps: In a four-necked reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin-containing DCPD phenol resin and 4 mol–8 mol of epichlorohydrin are added; the mixture is heated to 50–90°C and stirred for 1 hour; 100–400 g of alkaline catalyst C is uniformly added dropwise using a constant-pressure dropping funnel, with the addition time controlled at 60–120 minutes; the temperature is maintained during the addition process. The temperature is maintained at 50-90℃, and this temperature is maintained for 2-4 hours after the addition is completed. Excess epichlorohydrin is removed by vacuum distillation, and then dissolved in 1000-2000 mL of toluene. The temperature is then lowered to 40-60℃, and 20-200 g of alkaline catalyst C is added. The temperature is maintained at 40-80℃ for 60-180 minutes. The mixture is allowed to stand and separate into layers. The resin layer is retained, washed with water until neutral, and then the solvent is removed by rotary distillation to obtain the DCPD epoxy resin containing polyolefins.

[0008] The chemical structural formulas of the DCPD phenolic resin containing polyolefins are shown in formulas (4) to (6):

[0009] In equations (4) to (6): m is 0 to 10, and n is 30 to 80;

[0010] The DCPD phenolic resin containing polyolefin is one or a mixture of two or more of the structural formulas (4) to (6);

[0011] The alkaline catalyst C is one or a mixture of two of the following: a sodium hydroxide solution with a solid content of 30-70% and a potassium hydroxide solution with a solid content of 30-70%.

[0012] The solid content is defined as the percentage of solid components (solid parts) in the solution by weight of the total solution.

[0013] The prepared DCPD epoxy resin containing polyolefins has an equivalent range of 1000–2000 g / eq.

[0014] In another aspect of the present invention, the method for synthesizing the polyolefin-containing DCPD phenol resin is as follows: In a reactor equipped with a stirrer, a thermometer, and a condenser, 1 mol of polyolefin phenol and 100 g of cyclohexanone are added, followed by the addition of catalyst B at a weight of 1‰ to 1% of the weight of polyolefin phenol. The mixture is stirred (uniformly), heated to 80–140°C, and simultaneously 1–3 mol of DCPD is added to a constant pressure dropping funnel and added dropwise to the reactor over 1–2 hours. After the addition is completed, the temperature is maintained at 80–140°C for 2–4 hours. Then, the cyclohexanone is distilled off under reduced pressure, and the resin in the reactor is poured out while hot and cooled to obtain (brownish-colored) polyolefin-containing DCPD phenol resin.

[0015] The chemical structure of the polyolefin phenol is shown in formulas (7) to (9) below:

[0016] In equations (7) to (9): n is 10 to 40;

[0017] The polyolefin phenolic resin is one or a mixture of two or more of the structural formulas (7) to (9);

[0018] The catalyst B is one or a mixture of two or more of the following: boron trifluoride ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid.

[0019] The hydroxyl equivalent of the prepared DCPD phenol resin containing polyolefins ranges from 200 to 400 mgKOH / g.

[0020] The method for synthesizing polyalkenylphenol is as follows: In a reactor equipped with a stirrer, thermometer, and condenser, a certain amount of alkenylphenol and catalyst A, which accounts for 0.5% to 2% of the weight of alkenylphenol, are added. The temperature is raised to 60 to 120°C, and the reaction is carried out (after prepolymerization) for 1 to 3 hours. The temperature is then lowered to room temperature to obtain polyalkenylphenol.

[0021] The alkenylphenol is one or a mixture of two or more of 4-vinylphenol, 4-allylphenol, 3-allylphenol, and 3-(1-butenyl)phenol;

[0022] The catalyst A is one or a mixture of two or more of 2-methylimidazolium, 2-ethyl-4-methylimidazolium, and 2-methyl-4-phenylimidazolium;

[0023] The weight-average molecular weight of the polyolefin phenol prepared therein ranges from 1000 to 3000.

[0024] Another aspect of the present invention is a resin composition for copper clad laminates, characterized in that the resin composition for copper clad laminates is composed of 60-80 parts by weight of a polyolefin-containing DCPD epoxy resin, 10-20 parts by weight of a maleimide resin, 5-10 parts by weight of a phosphorus-containing phenolic resin, 0.1-0.5 parts by weight of an imidazole catalyst, and 23-73 parts by weight of methyl ethyl ketone.

[0025] The chemical structural formulas of the DCPD epoxy resin containing polyolefin are shown in (1) to (3);

[0026] In equations (1) to (3): m is 0 to 10, and n is 30 to 80;

[0027] The chemical structure of the maleimide resin is shown in formula (10) below:

[0028] In the formula: n is 0 to 10, R1 is -CH2-, -SO2, -O-, -CO-, -S2-, -(CH2)2-, -(CH2)4-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -,-(CH2) 12 -, , , , , , ;

[0029] R2 can be H, -CH3, -C2H5-, -C3H7-, -COOH, -NO2, -CH=CH2, or -CH2-CH=CH2. , tert-butyl, phenyl, methacryloyl; R3, R4 are H, -CH3;

[0030] The chemical structural formula of the phosphorus-containing phenolic resin is as follows (11):

[0031] In the formula, s ranges from 1 to 5;

[0032] The imidazole catalyst is one or a mixture of two or more of the following: imidazole, 2-methylimidazolium, 1-methylimidazolium, 1,2-dimethylimidazolium, 1,3-dimethylimidazolium, and 2,4-dimethylimidazolium.

[0033] The method for preparing the resin composition for copper clad laminates is as follows: 60-80 parts by weight of DCPD epoxy resin containing polyolefin, 10-20 parts by weight of maleimide resin, 5-10 parts by weight of phosphorus-containing phenolic resin, 0.1-0.5 parts by weight of imidazole catalyst and 23-73 parts by weight of butanone are mixed and stirred evenly at room temperature to obtain the resin composition for copper clad laminates.

[0034] The solid content (i.e., solid content) of the resin composition for copper clad laminates ranges from 60% to 76%.

[0035] Compared with the prior art, the present invention has the following features and beneficial effects:

[0036] (1) The present invention firstly uses alkenyl phenol and catalyst A to polymerize at high temperature to form polyallyl phenol, then uses DCPD, polyalkenyl phenol and catalyst B to react at high temperature to form DCPD phenol resin containing polyalkenyl; then it is epoxidized with epichlorohydrin and alkaline catalyst C under certain conditions to synthesize DCPD epoxy resin containing polyalkenyl; finally it is mixed with maleimide resin, phosphorus-containing phenolic resin, imidazole accelerator, inorganic filler and solvent to obtain a composition for copper clad laminate containing DCPD epoxy resin, thereby providing a composition for copper clad laminate containing polyalkenyl with low dielectric constant, low dielectric loss and high heat resistance, and its preparation method.

[0037] (2) The DCPD epoxy resin containing polyolefin synthesized in this invention has a lower dielectric constant and dielectric loss than ordinary DCPD epoxy resin because the low polarity polyolefin chain is introduced into the structure, which increases the molecular free volume.

[0038] (3) The resin composition for copper clad laminate of the present invention introduces phosphorus-containing phenolic resin as a curing agent for epoxy resin. This resin has a high phosphorus content (9%) and can act as a flame retardant. On the other hand, because phosphorus-containing phenolic resin produces very few hydroxyl groups, the product molecules have low polarity and excellent dielectric properties.

[0039] (4) Maleimide resin is introduced into the resin composition for copper clad laminate of the present invention. A highly heat-resistant imide ring is introduced into the composition structure, which further improves the heat resistance of the product. In addition, the symmetrical structure of maleimide further reduces the dielectric constant and dielectric loss of the product.

[0040] (5) The resin composition for copper clad laminates provided by the present invention, after lamination: dielectric constant ≤3.20; dielectric loss ≤0.003; heat resistance Td5%≥370℃, Tg≥200℃; flame retardancy: UL-V0 level; it has the characteristics of low dielectric constant, low dielectric loss, high glass transition temperature and good flame retardancy, and has excellent comprehensive performance, and can be used as a high-performance resin for copper clad laminates;

[0041] (6) The product preparation process of the present invention is simple, the procedure is simple, it is easy to operate, the product has good performance and strong practicality. Detailed Implementation

[0042] The embodiments given below are intended to further illustrate the present invention, but should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made to the present invention by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0043] Part 1: Preparation of DCPD epoxy resin containing polyolefin groups

[0044] 1.1 Preparation of polyolefin phenolic resin

[0045] Basic process: Preparation (synthesis) of polyalkenylphenol: In a reactor equipped with a stirrer, thermometer and condenser, a certain amount of alkenylphenol and 0.5% to 2% by weight of catalyst A are added. The temperature is raised to 60 to 120°C (temperature 1) and the prepolymerization reaction is carried out for 1 to 3 hours (time 1). The temperature is then lowered to room temperature to obtain polyalkenylphenol.

[0046] Table 1: Raw material dosage (g) and process parameters for the preparation of polyolefin phenolic resin in Examples 1-1 to 1-4

[0047]

[0048] 1.2 Preparation of DCPD phenolic resin containing polyolefin groups

[0049] Basic process: In a reactor equipped with a stirrer, thermometer, and condenser, add 1 mol of polyolefin phenol and 100 g of cyclohexanone, then add catalyst B at 1‰–1% of the weight of polyolefin phenol. Stir until homogeneous, and heat to 80–140°C (temperature 2). Simultaneously, add 1.2–3 mol of DCPD to a constant pressure dropping funnel and add it dropwise to the reactor over 1–2 hours (time 2). After the addition is complete, maintain the reaction at 80–140°C for 2–4 hours (time 3). Distill off the cyclohexanone under reduced pressure, pour the resin out of the bottle while hot, and after cooling, obtain a brownish-red DCPD phenol resin containing polyolefins.

[0050] Table 2: Raw material dosage (unit: mol) and process parameters for preparing polyolefin-containing DCPD phenolic resins in Examples 2-1 to 2-8

[0051]

[0052] 1.3 Preparation of DCPD epoxy resin containing polyolefin groups

[0053] Basic process: In a four-necked reactor equipped with a stirrer, thermometer, and condenser, add 1 mol of polyolefin-containing DCPD phenol resin and 4-8 mol of epichlorohydrin. Heat to 50-90℃ (Temperature 3) and stir for 1 hour. Using a constant-pressure dropping funnel, uniformly add 100-400 g of alkaline catalyst C1 over a period of 60-120 minutes, maintaining the temperature at 50-90℃ during the addition (Temperature 4). After the addition is complete, maintain this temperature for 2-4 hours (Time 4). Remove excess epichlorohydrin by vacuum distillation, dissolve in 1000-2000 mL of toluene, then cool to 40-60℃ (Temperature 5), add 20-200 g of alkaline catalyst C2, and maintain the temperature at 40-80℃ (Temperature 6) for 60-180 minutes (Time 5). Separate layers are formed; retain the resin layer. Wash the resin layer with water until neutral, then remove the solvent by rotation to obtain polyolefin-containing DCPD epoxy resin.

[0054] Table 3: Raw material dosage and process parameters for preparing polyolefin-containing DCPD epoxy resins in Examples 3-1 to 3-8

[0055]

[0056] Part Two: Formulation and Performance Results of Resin Compositions for Copper Clad Laminates

[0057] Formulation of resin composition for copper clad laminate: The resin composition for copper clad laminate is composed of 60-80 parts by weight of DCPD epoxy resin containing polyolefin, 10-20 parts by weight of maleimide resin, 5-10 parts by weight of phosphorus-containing phenolic resin, 0.1-0.5 parts by weight of imidazole catalyst and 23-73 parts by weight of butanone.

[0058] Table 4: Formulation of Resin Compositions for Copper Clad Laminates in Examples 4-1 to 4-8 (Unit: g)

[0059]

[0060] Table 5: Results of board performance of resin compositions for copper clad laminates in Examples 4-1 to 4-8

[0061]

[0062] The technical performance testing methods in Table 5 are as follows:

[0063] (1) Dielectric constant

[0064] The dielectric constant at 10 GHz was determined according to the method specified in section 2.5.5.9 of IPC-TM-650.

[0065] (2) Dielectric loss factor tangent

[0066] The dielectric loss at 10 GHz was determined according to the method specified in section 2.5.5.9 of IPC-TM-650.

[0067] (3) Glass transition temperature (Tg)

[0068] The determination was performed according to the differential scanning calorimetry (DSC) method specified in section 2.4.25 of IPC-TM-650.

[0069] (4) Thermal decomposition temperature (Td)

[0070] The determination was performed according to the method specified in 2.4.26 of IPC-TM-650.

[0071] (5) Flame retardancy

[0072] Refer to UL94 testing standards.

[0073] As shown in Table 5, the substrate obtained by applying the embodiments of the present invention exhibits excellent heat resistance, low dielectric constant and dielectric loss factor, and good flame retardancy. The compositions of the present invention can be used in laminates, integrated circuit packaging, high-frequency and high-speed copper-clad laminates, and high-density internet applications, showing broad application prospects. Example 5:

[0074] A DCPD epoxy resin containing polyolefin has a chemical structure containing a dicyclopentadiene ring, an epoxy ring and a polyolefin structure, and its chemical structural formula is shown in (1) to (3).

[0075] In equations (1) to (3): m is 0 to 10, and n is 30 to 80.

[0076] Example 6:

[0077] A method for preparing a polyolefin-containing DCPD epoxy resin includes the following steps: In a four-necked reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin-containing DCPD phenol resin and 4 mol of epichlorohydrin are added. The mixture is heated to 50°C and stirred for 1 hour. 100 g of alkaline catalyst C is added dropwise uniformly using a constant-pressure dropping funnel, with the addition time controlled at 60 min. The temperature is maintained at 50°C during the addition process, and the reaction is maintained at this temperature for 4 hours after the addition is completed. Excess epichlorohydrin is removed by vacuum distillation, and then dissolved in 1000 mL of toluene. The mixture is then cooled to 40°C, and 20 g of alkaline catalyst C is added. The reaction is maintained at 40°C for 180 min. The mixture is allowed to stand and separate into layers, retaining the resin layer. The resin layer is washed with water until neutral, and then the solvent is removed by rotary distillation to obtain the polyolefin-containing DCPD epoxy resin.

[0078] The alkaline catalyst C is a sodium hydroxide solution with a solid content of 70%.

[0079] Example 7:

[0080] A method for preparing a polyolefin-containing DCPD epoxy resin includes the following steps: In a four-necked reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin-containing DCPD phenol resin and 8 mol of epichlorohydrin are added. The mixture is heated to 90°C and stirred for 1 hour. 400 g of alkaline catalyst C is added dropwise uniformly using a constant-pressure dropping funnel, with the addition time controlled at 120 min. The temperature is maintained at 90°C during the addition process, and this temperature is maintained for 2 hours after the addition is completed. Excess epichlorohydrin is removed by vacuum distillation, and then dissolved in 2000 mL of toluene. The mixture is then cooled to 60°C, and 200 g of alkaline catalyst C is added. The temperature is maintained at 80°C for 60 min. The mixture is allowed to stand and separate into layers, retaining the resin layer. The resin layer is washed with water until neutral, and then the solvent is removed by rotary distillation to obtain the polyolefin-containing DCPD epoxy resin.

[0081] The alkaline catalyst C is a sodium hydroxide solution with a solid content of 30%.

[0082] Example 8:

[0083] A method for preparing a polyolefin-containing DCPD epoxy resin includes the following steps: In a four-necked reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin-containing DCPD phenol resin and 6 mol of epichlorohydrin are added. The mixture is heated to 70°C and stirred for 1 hour. 250 g of alkaline catalyst C is added dropwise uniformly using a constant-pressure dropping funnel, with the addition time controlled at 90 min. The temperature is maintained at 70°C during the addition process, and the reaction is maintained at this temperature for 3 hours after the addition is completed. Excess epichlorohydrin is removed by vacuum distillation, and then dissolved in 1500 mL of toluene. The mixture is then cooled to 50°C, and 110 g of alkaline catalyst C is added. The reaction is maintained at 60°C for 120 min. The mixture is allowed to stand and separate into layers, retaining the resin layer. The resin layer is washed with water until neutral, and then the solvent is removed by rotary distillation to obtain the polyolefin-containing DCPD epoxy resin.

[0084] The alkaline catalyst C is a sodium hydroxide solution with a solid content of 45%.

[0085] In the above embodiments 6-8:

[0086] The chemical structural formulas of the DCPD phenolic resin containing polyolefins are shown in formulas (4) to (6):

[0087] In equations (4) to (6): m is 0 to 10, and n is 30 to 80;

[0088] The DCPD phenolic resin containing polyolefin is one or a mixture of two or more of the structural formulas (4) to (6);

[0089] The solid content is defined as the percentage of solids in the solution by weight of the total solution.

[0090] The obtained DCPD epoxy resin containing polyolefins has an equivalent range of 1000–2000 g / eq.

[0091] Example 9:

[0092] A method for preparing a polyolefin-containing DCPD epoxy resin, wherein the method for synthesizing the polyolefin-containing DCPD phenol resin is as follows: In a reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin phenol and 100 g of cyclohexanone are added, followed by the addition of catalyst B at a weight of 1‰ of the weight of polyolefin phenol. The mixture is stirred (unified), heated to 80°C, and simultaneously 1 mol of DCPD is added to a constant pressure dropping funnel and added dropwise to the reactor over 1 hour. After the addition is completed, the temperature is maintained at 80°C for 2 hours. Then, the cyclohexanone is distilled off under reduced pressure, and the resin in the reactor is poured out while hot and cooled to obtain (brownish-colored) polyolefin-containing DCPD phenol resin; other steps are the same as in any of Examples 6-8, omitted.

[0093] Example 10:

[0094] A method for preparing a polyolefin-containing DCPD epoxy resin, wherein the method for synthesizing the polyolefin-containing DCPD phenol resin is as follows: In a reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin phenol and 100 g of cyclohexanone are added, followed by the addition of catalyst B at 1% of the weight of polyolefin phenol. The mixture is stirred (unified), heated to 140°C, and simultaneously 3 mol of DCPD is added to a constant pressure dropping funnel and added dropwise to the reactor over 2 hours. After the addition is completed, the temperature is maintained at 140°C for 4 hours. Then, the cyclohexanone is distilled off under reduced pressure, and the resin in the reactor is poured out while hot and cooled to obtain (brownish-colored) polyolefin-containing DCPD phenol resin; other steps are the same as in any of Examples 6-8, omitted.

[0095] Example 11:

[0096] A method for preparing a polyolefin-containing DCPD epoxy resin, wherein the method for synthesizing the polyolefin-containing DCPD phenol resin is as follows: In a reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin phenol and 100 g of cyclohexanone are added, followed by the addition of catalyst B at a weight of 0.5% of the weight of polyolefin phenol. The mixture is stirred (unified), heated to 110°C, and simultaneously 2 mol of DCPD is added to a constant pressure dropping funnel and added dropwise to the reactor over 1.5 h. After the addition is completed, the temperature is maintained at 110°C for 3 h. Then, the cyclohexanone is distilled off under reduced pressure, and the resin in the reactor is poured out while hot and cooled to obtain (brownish-colored) polyolefin-containing DCPD phenol resin; other steps are the same as in any of Examples 6-8, omitted.

[0097] In the above embodiments 9-11:

[0098] The chemical structure of the polyolefin phenol is shown in formulas (7) to (9) below:

[0099] In equations (7) to (9): n is 10 to 40;

[0100] The polyolefin phenolic resin is one or a mixture of two or more of the structural formulas (7) to (9);

[0101] The catalyst B is one or a mixture of two or more of the following: boron trifluoride ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid.

[0102] The hydroxyl equivalent of the prepared DCPD phenol resin containing polyolefins is in the range of 200–400 mgKOH / g.

[0103] Example 12:

[0104] A method for preparing a DCPD epoxy resin containing polyolefin, wherein the polyolefin phenol is synthesized by: adding a polyolefin phenol and a catalyst A comprising 0.5% by weight of the polyolefin phenol in a reactor equipped with a stirrer, a thermometer, and a condenser; heating to 60°C and reacting (after prepolymerization) for 3 hours; cooling to room temperature to obtain polyolefin phenol; other steps are the same as in any of Examples 9-11, omitted.

[0105] Example 13:

[0106] A method for preparing a DCPD epoxy resin containing polyolefin, wherein the polyolefin phenol is synthesized by: adding a polyolefin phenol and a catalyst A comprising 2% by weight of the polyolefin phenol in a reactor equipped with a stirrer, a thermometer, and a condenser; heating to 120°C and reacting for 1 hour (after prepolymerization); cooling to room temperature to obtain polyolefin phenol; other steps are the same as in any of Examples 9-11, omitted.

[0107] Example 14:

[0108] A method for preparing a DCPD epoxy resin containing polyolefin, wherein the polyolefin phenol is synthesized by: adding a polyolefin phenol and a catalyst A comprising 1.2% by weight of the polyolefin phenol in a reactor equipped with a stirrer, a thermometer, and a condenser; heating to 90°C and reacting (after prepolymerization) for 2 hours; cooling to room temperature to obtain polyolefin phenol; other steps are the same as in any of Examples 9-11, omitted.

[0109] In the above embodiments 12-14:

[0110] The alkenylphenol is one or a mixture of two or more of 4-vinylphenol, 4-allylphenol, 3-allylphenol, and 3-(1-butenyl)phenol;

[0111] The catalyst A is one or a mixture of two or more of 2-methylimidazolium, 2-ethyl-4-methylimidazolium, and 2-methyl-4-phenylimidazolium;

[0112] The weight-average molecular weight of the prepared polyolefin phenol is in the range of 1000 to 3000.

[0113] Example 15:

[0114] A resin composition for copper clad laminates, comprising 60 parts by weight of a polyolefin-containing DCPD epoxy resin, 10 parts by weight of a maleimide resin, 5 parts by weight of a phosphorus-containing phenolic resin, 0.1 parts by weight of an imidazole catalyst, and 10 parts by weight of methyl ethyl ketone; other components are the same as described in Examples 6-11, and are omitted.

[0115] Example 16:

[0116] A resin composition for copper clad laminates, comprising 80 parts by weight of a polyolefin-containing DCPD epoxy resin, 20 parts by weight of a maleimide resin, 10 parts by weight of a phosphorus-containing phenolic resin, 0.5 parts by weight of an imidazole catalyst, and 20 parts by weight of methyl ethyl ketone; other components are the same as described in Examples 6-11, and are omitted.

[0117] Example 17:

[0118] A resin composition for copper clad laminates, comprising 70 parts by weight of a polyolefin-containing DCPD epoxy resin, 15 parts by weight of a maleimide resin, 7.5 parts by weight of a phosphorus-containing phenolic resin, 0.3 parts by weight of an imidazole catalyst, and 15 parts by weight of methyl ethyl ketone; the other components are the same as described in Examples 6-11, and are omitted.

[0119] In the above embodiments 15-17:

[0120] The chemical structural formulas of the DCPD epoxy resin containing polyolefin are shown in (1) to (3);

[0121] In equations (1) to (3): m is 0 to 10, and n is 30 to 80;

[0122] The chemical structure of the maleimide resin is shown in formula (10) below:

[0123]

[0124] In the formula: n is 0 to 10, R1 is -CH2-, -SO2, -O-, -CO-, -S2-, -(CH2)2-, -(CH2)4-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -,-(CH2) 12 -, , , , , , ;

[0125] R2 can be H, -CH3, -C2H5-, -C3H7-, -COOH, -NO2, -CH=CH2, or -CH2-CH=CH2. , tert-butyl, phenyl, methacryloyl; R3, R4 are H, -CH3;

[0126] The chemical structural formula of the phosphorus-containing phenolic resin is as follows (11):

[0127] In the formula, s ranges from 1 to 5;

[0128] The imidazole catalyst is one or a mixture of two or more of the following: imidazole, 2-methylimidazolium, 1-methylimidazolium, 1,2-dimethylimidazolium, 1,3-dimethylimidazolium, and 2,4-dimethylimidazolium.

[0129] Example 18:

[0130] A resin composition for copper clad laminates is prepared by mixing and stirring a polyolefin-containing DCPD epoxy resin, maleimide resin, phosphorus-containing phenolic resin, imidazole catalyst, and butanone at room temperature until homogeneous, thereby obtaining the resin composition for copper clad laminates; other steps are the same as any of Examples 15-17, and are omitted.

[0131] In the above embodiments: unless otherwise specified, the percentage examples used are mass (weight) percentage examples or percentage examples known to those skilled in the art; unless otherwise specified, the proportions used are mass (weight) proportions; the weight parts can all be grams or kilograms.

[0132] In the above embodiments, the process parameters (temperature, time, concentration, etc.) and the dosage values ​​of each component in each step are ranges, and any point can be applied.

[0133] The technical contents of this invention and the above embodiments that are not specifically described are the same as those of the prior art, and the raw materials are all commercially available products.

[0134] The present invention is not limited to the above embodiments; all embodiments described herein can be implemented and have the aforementioned good effects.

Claims

1. A DCPD epoxy resin containing polyalkenyl groups, characterized by: The chemical structure of the epoxy resin contains a dicyclopentadiene ring, an epoxy ring and a polyolefin structure, and its chemical structural formula is one or a mixture of two or more shown in (1) to (3). In equations (1) to (3): m is 0 to 10, m is not 0, and n is 30 to 80.

2. A method for preparing a polyolefin-containing DCPD epoxy resin, characterized by the following steps: In a four-necked reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin-containing DCPD phenol resin and 4 mol–8 mol of epichlorohydrin are added; the temperature is raised to 50–90°C and stirred for 1 hour; 100–400 g of alkaline catalyst C is uniformly added dropwise using a constant-pressure dropping funnel, with the dropping time controlled at 60–120 minutes, and the temperature maintained during the dropping process. After the addition is complete, maintain this temperature for 2-4 hours. Remove excess epichlorohydrin by vacuum distillation, then dissolve it in 1000-2000 mL of toluene. Cool the temperature to 40-60°C, add 20-200 g of alkaline catalyst C, and maintain the temperature at 40-80°C for 60-180 minutes. Allow the mixture to stand and separate into layers, retaining the resin layer. Wash the resin layer with water until neutral, and then remove the solvent by rotary distillation to obtain the DCPD epoxy resin containing polyolefins. The chemical structural formulas of the DCPD phenolic resin containing polyolefins are shown in formulas (4) to (6): In equations (4) to (6): m is 0 to 10, m is not 0, and n is 30 to 80; The DCPD phenolic resin containing polyolefin is one or a mixture of two or more of the structural formulas (4) to (6); The alkaline catalyst C is one or a mixture of two of the following: a sodium hydroxide solution with a solid content of 30-70% and a potassium hydroxide solution with a solid content of 30-70%. The equivalent range of the prepared DCPD epoxy resin containing polyolefin is 1000-2000 g / eq; The method for synthesizing the polyolefin-containing DCPD phenol resin is as follows: In a reactor equipped with a stirrer, thermometer, and condenser, 1 mol of polyolefin phenol and 100 g of cyclohexanone are added, followed by the addition of catalyst B, which accounts for 1‰ to 1% of the weight of polyolefin phenol. The mixture is stirred and heated to 80–140°C. Simultaneously, 1–3 mol of DCPD is added to a constant-pressure dropping funnel and added dropwise to the reactor over 1–2 hours. After the addition is completed, the temperature is maintained at 80–140°C for 2–4 hours. Then, the cyclohexanone is distilled off under reduced pressure, and the resin in the reactor is poured out while hot and cooled to obtain the polyolefin-containing DCPD phenol resin. The chemical structure of the polyolefin phenol is shown in formulas (7) to (9) below: In equations (7) to (9): n is 10 to 40; The polyolefin phenolic resin is one or a mixture of two or more of the structural formulas (7) to (9); The catalyst B is one or a mixture of two or more of the following: boron trifluoride ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, tin tetrachloride, ferric chloride, concentrated sulfuric acid, and phosphoric acid. The hydroxyl equivalent of the prepared DCPD phenol resin containing polyolefins ranges from 200 to 400 mgKOH / g.

3. The process for preparing a polyalkenyl-containing DCPD epoxy resin according to Claim 2, characterized by: The method for synthesizing polyalkenylphenol is as follows: In a reactor equipped with a stirrer, a thermometer, and a condenser, add alkenylphenol and catalyst A, which accounts for 0.5% to 2% of the weight of alkenylphenol, heat to 60 to 120°C, react for 1 to 3 hours, and then cool to room temperature to obtain polyalkenylphenol. The alkenylphenol is one or a mixture of two or more of 4-vinylphenol, 4-allylphenol, and 3-(1-butenyl)phenol; The catalyst A is one or a mixture of two or more of 2-methylimidazolium, 2-ethyl-4-methylimidazolium, and 2-methyl-4-phenylimidazolium; The weight-average molecular weight of the polyolefin phenol prepared therein ranges from 1000 to 3000.

4. A resin composition for a copper-clad plate, characterized by: The resin composition for copper clad laminates is composed of 60-80 parts by weight of DCPD epoxy resin containing polyolefin, 10-20 parts by weight of maleimide resin, 5-10 parts by weight of phosphorus-containing phenolic resin, 0.1-0.5 parts by weight of imidazole catalyst and 23-73 parts by weight of butanone. The chemical structural formula of the DCPD epoxy resin containing polyolefin is one or a mixture of two or more of the formulas shown in (1) to (3). In equations (1) to (3): m is 0 to 10, m is not 0, and n is 30 to 80; The chemical structure of the maleimide resin is shown in formula (10): In the formula: n is 0 to 10, R1 is -CH2-, -SO2, -O-, -CO-, -(CH2)2-, -(CH2)4-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -,-(CH2) 12 -, , , , , ; R2 can be H, -CH3, -C2H5, -C3H7, -COOH, -NO2, -CH=CH2, or -CH2-CH=CH2. , tert-butyl, phenyl, methacryloyl; R3, R4 are H, -CH3; The chemical structural formula of the phosphorus-containing phenolic resin is as follows (11): In the formula, s ranges from 1 to 5; The imidazole catalyst is one or a mixture of two or more of the following: imidazole, 2-methylimidazolium, 1-methylimidazolium, 1,2-dimethylimidazolium, 1,3-dimethylimidazolium, and 2,4-dimethylimidazolium.

5. The resin composition for copper-clad laminates according to claim 4, characterized in that: The method for preparing the resin composition for copper clad laminates is as follows: 60-80 parts by weight of DCPD epoxy resin containing polyolefin, 10-20 parts by weight of maleimide resin, 5-10 parts by weight of phosphorus-containing phenolic resin, 0.1-0.5 parts by weight of imidazole catalyst and 23-73 parts by weight of butanone are mixed and stirred evenly at room temperature to obtain the resin composition for copper clad laminates.

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