Self-toughening hydrocarbon copolymer for high-frequency high-speed copper-clad plate and preparation method of self-toughening hydrocarbon copolymer

Abstract

The invention relates to the technical field of hydrocarbon resin, in particular to a self-toughening hydrocarbon copolymer for a high-frequency high-speed copper-clad plate and a preparation method of the self-toughening hydrocarbon copolymer. According to the invention, divinyl benzene, styrene and 4-tert-butyl styrene are used as main raw materials, and atom transfer radical polymerization is adopted to prepare the hydrocarbon copolymer containing vinyl. On the basis, a styrene-butadiene-styrene block copolymer (SBS) is directly added in a polymerization reaction to prepare the hydrocarbon copolymer with a self-toughening effect, and the hydrocarbon copolymer shows better formability. And finally, preparing a glue solution by using the prepared hydrocarbon copolymer, di-tert-butylperoxy isopropyl benzene, an antioxidant 1010 and xylene as raw materials, and heating, curing and molding to obtain a finished product. The prepared finished product has good heat resistance, water absorption, dielectric property and thermal expansion coefficient, and can be applied to the field of high-frequency and high-speed copper-clad plates.

Description

Technical Field

[0001] The invention belongs to the field of electronic resin synthesis, and in particular relates to a synthesis method of a vinyl-containing hydrocarbon resin and a self-toughening hydrocarbon resin and applications thereof in high-frequency and high-speed copper-clad laminates. Background Art

[0002] With the rapid development of electronic technology, the increase in information communication in recent years has brought unprecedented opportunities for the research and development of high-performance printed circuit boards (PCBs). High-frequency and high-speed PCBs are required in the fields of fifth-generation (5G) microwave components, automotive electronics, satellite broadcast communications, radars and other high-frequency communication devices. Copper clad laminate (CCL), as an important raw material for PCB, is the basic structural basis for connecting load electronic components. CCL is composed of an insulating layer and copper foil, and its performance is mainly affected by the insulating layer. Among them, the insulating layer of CCL is a polymer composite material, mainly composed of polymer resin, ceramic powder, glass fabric, etc. Therefore, in order to meet the high-frequency and high-speed information transmission capabilities of PCB, the development of polymer composite materials with lower dielectric constant (Dk) and low dielectric loss (Df) has become the key to the problem.

[0003] Among them, the modified epoxy resin, cyanate resin and polyimide all contain polar groups in their structures, which makes their dielectric properties unable to meet the requirements of high-frequency applications. Polytetrafluoroethylene resin and polyphenylene ether resin have become common polymer matrices for high-frequency and high-speed PCBs due to their excellent dielectric properties. However, their disadvantages are also obvious, such as the high coefficient of thermal expansion (CTE) of polytetrafluoroethylene, difficult processing, poor rigidity and high cost; the high melting temperature and high melt viscosity of polyphenylene ether resin make it difficult to process thermoplastics, and it is easily corroded by solvents (such as halogenated hydrocarbons or aromatic hydrocarbons used in CCL cleaning processing), and it needs to be modified to improve its performance. Hydrocarbon resin itself is a non-polar or low-polar polymer with excellent dielectric properties (dielectric constant of 2.2-2.8 at 1MHz, tanδ of 0.0001-0.0006), as well as good mechanical properties, processing properties, thermal stability and water resistance, etc. It is a high-frequency and high-speed matrix resin with great application prospects.

[0004] However, the current research on hydrocarbon resins generally has the problems of high thermal expansion coefficient and poor heat resistance. It is of great significance to develop hydrocarbon resin substrates with both low thermal expansion coefficient and low dielectric loss. Summary of the invention

[0005] The purpose of the present invention is to provide a method for synthesizing a hydrocarbon copolymer, and to develop a method for synthesizing a hydrocarbon copolymer containing vinyl and a hydrocarbon copolymer with self-toughening by atom transfer radical polymerization. The self-toughening hydrocarbon copolymer developed by the present invention has excellent heat resistance, compatibility, formability, dimensional stability, water absorption and dielectric properties, and can be used in the field of high-frequency and high-speed copper clad laminates.

[0006] The present invention is achieved through the following technical solutions:

[0007] A method for preparing a vinyl hydrocarbon copolymer for high-frequency and high-speed copper-clad laminates comprises the following steps:

[0008] S1: Divinylbenzene, styrene, 4-tert-butylstyrene, ethyl 2-bromoisobutyrate, N,N,N',N',N''-pentamethyldiethylenetriamine, cupric bromide and xylene were placed in a three-necked flask and mixed evenly, and nitrogen was passed through for 20-30 minutes; cuprous bromide was added to the reaction system, and nitrogen was passed through for 15-20 minutes; after the ventilation was completed, heating was performed to start the polymerization reaction.

[0009] S2: Pour the reactant solution into a column filled with neutral alumina, remove impurities to obtain a clear reactant solution, gradually add the solution into 7-10 times of ice methanol solution to produce a white precipitate; filter and dry the white precipitate to obtain a vinyl-containing hydrocarbon copolymer.

[0010] S3: Weigh the following raw materials in parts by weight: 100 parts of vinyl hydrocarbon copolymer, 2 parts of di-tert-butyl peroxide isopropylbenzene, 2 parts of antioxidant 1010, and 100 parts of xylene; mix the above raw materials evenly to obtain hydrocarbon resin glue; pour the glue into a tetrafluoroethylene mold, place it in an oven for heating and curing to obtain a finished product.

[0011] Furthermore, the molar ratio of divinylbenzene:4-tert-butylstyrene:styrene is 1:0~0.6:3; the molar ratio of the total mole of divinylbenzene, styrene and 4-tert-butylstyrene to ethyl 2-bromoisobutyrate, N,N,N',N',N''-pentamethyldiethylenetriamine, cupric bromide, cuprous bromide and xylene is 200:2:0.125:0.5:660.

[0012] Furthermore, the reaction temperature is 90° C. and the reaction time is 24 h.

[0013] Furthermore, the curing program temperature is 80°C / 2h, 100°C / 2h, 120°C / 2h, 140°C / 2h, 160°C / 2h, 180°C / 1h.

[0014] Further, the hydrocarbon copolymer with self-toughening is obtained by the following steps:

[0015] S1: Place hydrocarbon resin and xylene in a three-necked flask and stir until uniformly dispersed; then add divinylbenzene, styrene, 4-tert-butylstyrene, ethyl 2-bromoisobutyrate, N,N,N',N',N''-pentamethyldiethylenetriamine and cupric bromide, mix evenly, and pass nitrogen for 20-30 minutes; add cuprous bromide to the reaction system, and then pass nitrogen for 15-20 minutes; after the ventilation is completed, heat and start the polymerization reaction.

[0016] S2: Pour the reactant solution into a column filled with neutral alumina, remove impurities to obtain a clear reactant solution, gradually add the solution into 7-10 times of ice methanol solution to produce a white precipitate; filter and dry the white precipitate to obtain a self-toughening hydrocarbon copolymer.

[0017] S3: Weigh the following raw materials in parts by weight: 100 parts of self-toughening hydrocarbon copolymer, 2 parts of di-tert-butyl peroxide isopropylbenzene, 2 parts of antioxidant 1010, and 100 parts to 150 parts of xylene; mix the above raw materials evenly to obtain hydrocarbon resin glue; pour the glue into a tetrafluoroethylene mold, place it in an oven for heating and curing to obtain a finished product.

[0018] Furthermore, the hydrocarbon resin is styrene-butadiene-styrene copolymer.

[0019] Furthermore, the total mass ratio of hydrocarbon resin to divinylbenzene, styrene and 4-tert-butylstyrene is 1:15~45, and the molar ratio of divinylbenzene, 4-tert-butylstyrene and styrene is 1:0.3:3; the molar ratio of the total mole of divinylbenzene, styrene and 4-tert-butylstyrene to ethyl 2-bromoisobutyrate, N,N,N',N',N''-pentamethyldiethylenetriamine, cupric bromide, cuprous bromide and xylene is 200:2:0.125:0.5:660.

[0020] Furthermore, the reaction temperature is 90° C. and the reaction time is 24 h.

[0021] Furthermore, the curing program temperature is 80°C / 2h, 100°C / 2h, 120°C / 2h, 140°C / 2h, 160°C / 2h, 180°C / 1h.

[0022] Beneficial effects of the present invention:

[0023] 1. The present invention provides a method for synthesizing vinyl-containing hydrocarbon copolymers. Using divinylbenzene, styrene and 4-tert-butylstyrene as raw materials, an atom transfer radical polymerization (ATRP) reaction is developed to synthesize such vinyl-containing terpolymers. These copolymers have reactive vinyl groups and highly branched structures, which contribute to their excellent processing properties. The cured resin exhibits good dielectric properties (Dk=2.29, tanδ=0.0036 at a frequency of 10 GHz) and has high thermal stability (Tg>175°C).

[0024] 2. The present invention innovatively directly adds styrene-butadiene-styrene (SBS) during the polymerization process to prepare a hydrocarbon copolymer with self-toughening effect. The hydrocarbon copolymer with self-toughening effect exhibits good compatibility and formability, and also has excellent heat resistance, water absorption and dielectric properties, and has excellent comprehensive performance, and has great application prospects in the field of high-frequency and high-speed copper-clad laminate materials. DETAILED DESCRIPTION

[0025] The present invention will be further described in detail with reference to the following examples, but these examples are not intended to limit the scope of the present invention.

[0026] Example 1

[0027] 40 mmol (5.2 g) of divinylbenzene, 12 mmol (1.92 g) of 4-tert-butylstyrene, 148 mmol (15.4 g) of styrene, 2 mmol (0.39 g) of ethyl 2-bromoisobutyrate, 1 mmol (0.173 g) of N,N,N',N',N''-pentamethyldiethylenetriamine, 0.125 mmol (0.0278 g) of cupric bromide and 660 mmol (70 g) of xylene were added into a 250 ml three-necked flask, and nitrogen was passed through for 20 min; 0.5 mmol (0.0717 g) of cuprous bromide was added into the reaction system under a nitrogen atmosphere, and nitrogen was continued to be passed through for 15 min. After the ventilation was completed, the reaction was carried out at 90°C for 24 h. The reactant solution was poured into a column filled with neutral alumina, and impurities were removed to obtain a clear reactant solution, which was gradually added into 7-10 times ice methanol solution to produce a white precipitate; the white precipitate was filtered and dried to obtain 10.2 g of vinyl-containing hydrocarbon copolymer A.

[0028] The M of the obtained hydrocarbon copolymer A n is 7664, M w is 28842, M w / M n The hydrocarbon copolymer A is soluble in toluene, xylene, tetrahydrofuran and dichloromethane (solid content above 50%), and no gel formation is observed.

[0029] 2g hydrocarbon copolymer A, 0.04g di-tert-butyl peroxide isopropylbenzene and 0.02g antioxidant 1010 were dissolved in 2g xylene and stirred at 60°C for 2h. The evenly mixed resin solution was poured into a tetrafluoroethylene mold and dried naturally for 24h. Finally, it was put into an oven and cured at 80°C / 2h, 100°C / 2h, 120°C / 2h, 140°C / 2h, 160°C / 2h and 180°C / 1h to obtain various test samples.

[0030] The thermosetting hydrocarbon resin prepared according to the above formula and process has the following performance indicators: dielectric constant 2.29 (10GHz), dielectric loss tangent 0.0036 (10GHz), water absorption 0.2%, thermal decomposition temperature Td 5％ The glass transition temperature is 372°C, the glass transition temperature is 176.4°C, and the linear thermal expansion coefficient CTE (room temperature - 100°C) is 104ppm / °C.

[0031] Example 2

[0032] 0.5 g SBS and 660 mmol (70 g) of xylene were added to a 250 ml three-necked flask and mixed evenly. Then, 40 mmol (5.2 g) of divinylbenzene, 12 mmol (1.92 g) of 4-tert-butylstyrene, 148 mmol (15.4 g) of styrene, 2 mmol (0.39 g) of ethyl 2-bromoisobutyrate, 1 mmol (0.173 g) of N,N,N',N',N''-pentamethyldiethylenetriamine, and 0.125 mmol (0.0278 g) of cupric bromide were added to the three-necked flask, and nitrogen was introduced for 20 min. Under a nitrogen atmosphere, 0.5 mmol (0.0717 g) of cuprous bromide was added to the reaction system, and nitrogen was continued to be introduced for 15 min. After the ventilation was completed, the reaction was carried out at 90°C for 24 h. The reactant solution was poured into a column filled with neutral alumina, and impurities were removed to obtain a clear reactant solution, which was gradually added into 7-10 times ice methanol solution to produce a white precipitate; the white precipitate was filtered and dried to obtain 10.1 g of self-toughening hydrocarbon copolymer B.

[0033] Self-toughened hydrocarbon copolymer B n 16732, M w is 62645, M w / M n The hydrocarbon copolymer B is soluble in toluene, xylene, tetrahydrofuran and dichloromethane (solid content above 50%), and no gel formation is observed.

[0034] 2g of self-toughening hydrocarbon copolymer B, 0.04g of di-tert-butyl peroxide isopropylbenzene and 0.02g of antioxidant 1010 were dissolved in 2g of xylene and stirred at 60°C for 2h. The evenly mixed resin solution was poured into a tetrafluoroethylene mold and dried naturally for 24h. Finally, it was put into an oven and cured at 80°C / 2h, 100°C / 2h, 120°C / 2h, 140°C / 2h, 160°C / 2h and 180°C / 1h to obtain various test samples.

[0035] The thermosetting hydrocarbon resin prepared according to the above formula and process has the following performance indicators: dielectric constant 2.35 (10GHz), dielectric loss tangent 0.0041 (10GHz), water absorption 0.25%, thermal decomposition temperature Td 5％ The glass transition temperature is 377°C, the glass transition temperature is 165.4°C, and the linear thermal expansion coefficient CTE (room temperature - 100°C) is 115ppm / °C.

[0036] Example 3

[0037] 1g SBS and 660mmol (70g) of xylene were added into a 250ml three-necked flask and mixed evenly, then 40mmol (5.2g) of divinylbenzene, 12mmol (1.92g) of 4-tert-butylstyrene, 148mmol (15.4g) of styrene, 2mmol (0.39g) of ethyl 2-bromoisobutyrate, 1mmol (0.173g) of N,N,N',N',N''-pentamethyldiethylenetriamine, and 0.125mmol (0.0278g) of cupric bromide were added into the three-necked flask, and nitrogen was introduced for 20min; 0.5mmol (0.0717g) of cuprous bromide was added into the reaction system under a nitrogen atmosphere, and nitrogen was continuously introduced for 15min. After the ventilation was completed, the mixture was reacted at 90°C for 24h. The reactant solution was poured into a column filled with neutral alumina, and impurities were removed to obtain a clear reactant solution, which was gradually added into 7-10 times ice methanol solution to produce a white precipitate; the white precipitate was filtered and dried to obtain 10.5 g of self-toughened hydrocarbon copolymer C.

[0038] Self-toughened hydrocarbon copolymer C n is 18634, M w is 75675, M w / M n The hydrocarbon copolymer C is soluble in toluene, xylene, tetrahydrofuran and dichloromethane (solid content above 50%), and no gel formation is observed.

[0039] 2g of self-toughening hydrocarbon copolymer C, 0.04g of di-tert-butyl peroxide isopropylbenzene and 0.02g of antioxidant 1010 were dissolved in 2g of xylene and stirred at 60°C for 2h. The evenly mixed resin solution was poured into a tetrafluoroethylene mold and dried naturally for 24h. Finally, it was put into an oven and cured at 80°C / 2h, 100°C / 2h, 120°C / 2h, 140°C / 2h, 160°C / 2h and 180°C / 1h to obtain various test samples.

[0040] The thermosetting hydrocarbon resin prepared according to the above formula and process has the following performance indicators: dielectric constant 2.38 (10GHz), dielectric loss tangent 0.0044 (10GHz), water absorption rate 0.33%, thermal decomposition temperature Td 5％ The glass transition temperature is 363°C, the glass transition temperature is 160°C, and the linear thermal expansion coefficient CTE (room temperature - 100°C) is 118.6ppm / °C.

[0041] Example 4

[0042] 1.5 g SBS and 660 mmol (70 g) of xylene were added to a 250 ml three-necked flask and mixed evenly, and then 40 mmol (5.2 g) of divinylbenzene, 12 mmol (1.92 g) of 4-tert-butylstyrene, 148 mmol (15.4 g) of styrene, 2 mmol (0.39 g) of ethyl 2-bromoisobutyrate, 1 mmol (0.173 g) of N,N,N',N',N''-pentamethyldiethylenetriamine, and 0.125 mmol (0.0278 g) of cupric bromide were added to the three-necked flask, and nitrogen was passed through for 20 min; 0.5 mmol (0.0717 g) of cuprous bromide was added to the reaction system under a nitrogen atmosphere, and nitrogen was continued to be passed through for 15 min. After the ventilation was completed, the reaction was carried out at 90°C for 24 h. The reactant solution was poured into a column filled with neutral alumina, and impurities were removed to obtain a clear reactant solution, which was gradually added into a 7-10 times ice methanol solution to produce a white precipitate; the white precipitate was filtered and dried to obtain 9.8 g of self-toughened hydrocarbon copolymer D;

[0043] Self-toughened hydrocarbon copolymer D n is 19726, M w is 82381, M w / M n The hydrocarbon copolymer D is soluble in toluene, xylene, tetrahydrofuran and dichloromethane (solid content above 40%), and no gel formation is observed.

[0044] 2g of self-toughening hydrocarbon copolymer D, 0.04g of di-tert-butyl peroxide isopropylbenzene and 0.02g of antioxidant 1010 were dissolved in 3g of xylene and stirred at 60°C for 2h. The evenly mixed resin solution was poured into a tetrafluoroethylene mold and dried naturally for 24h. Finally, it was put into an oven and cured at 80°C / 2h, 100°C / 2h, 120°C / 2h, 140°C / 2h, 160°C / 2h and 180°C / 1h to obtain various test samples.

[0045] The thermosetting hydrocarbon resin prepared according to the above formula and process has the following performance indicators: dielectric constant 2.42 (10GHz), dielectric loss tangent 0.0048 (10GHz), water absorption rate 0.44%, thermal decomposition temperature Td 5％ The temperature of the glass transition temperature is 361°C, the glass transition temperature is 155.5°C, and the coefficient of linear thermal expansion CTE (room temperature - 100°C) is 119.2ppm / °C.

[0046] Comparative Example 1

[0047] 40 mmol (5.2 g) of divinylbenzene, 24 mmol (3.84 g) of 4-tert-butylstyrene, 148 mmol (15.4 g) of styrene, 2 mmol (0.39 g) of ethyl 2-bromoisobutyrate, 1 mmol (0.173 g) of N,N,N',N',N''-pentamethyldiethylenetriamine, 0.125 mmol (0.0278 g) of cupric bromide and 660 mmol (70 g) of xylene were added into a 250 ml three-necked flask, and nitrogen was passed through for 20 min; 0.5 mmol (0.0717 g) of cuprous bromide was added into the reaction system under a nitrogen atmosphere, and nitrogen was continued to be passed through for 15 min. After the ventilation was completed, the reaction was carried out at 90°C for 24 h. The reactant solution was poured into a column filled with neutral alumina, and impurities were removed to obtain a clear reactant solution, which was gradually added into 7-10 times ice methanol solution to produce a white precipitate; the white precipitate was filtered and dried to obtain 10.2 g of vinyl-containing hydrocarbon copolymer E.

[0048] M of hydrocarbon copolymer E n 8499, M w is 40787, M w / M n The hydrocarbon copolymer E is soluble in toluene, xylene, tetrahydrofuran and dichloromethane (solid content above 40%), and no gel formation is observed.

[0049] Compared with Example 1, the proportion of 4-tert-butylstyrene monomer in Comparative Example 1 is large, the molecular weight of the synthesized polymer is slightly increased, and the yield of the copolymer is not significantly increased.

[0050] Comparative Example 2

[0051] 50 mmol (6.5 g) of divinylbenzene, 150 mmol (15.6 g) of styrene, 2 mmol (0.39 g) of ethyl 2-bromoisobutyrate, 1 mmol (0.173 g) of N,N,N',N',N''-pentamethyldiethylenetriamine, 0.125 mmol (0.0278 g) of cupric bromide and 660 mmol (70 g) of xylene were added into a 250 ml three-necked flask, and nitrogen was passed through for 20 min; 0.5 mmol (0.0717 g) of cuprous bromide was added into the reaction system under a nitrogen atmosphere, and nitrogen was continued to be passed through for 15 min. After the ventilation was completed, the reaction was carried out at 90°C for 24 h. The reactant solution was poured into a column filled with neutral alumina, and impurities were removed to obtain a clear reactant solution, which was gradually added into 7-10 times ice methanol solution to produce a white precipitate; the white precipitate was filtered and dried to obtain 3.98 g of vinyl-containing hydrocarbon copolymer F.

[0052] M of hydrocarbon copolymer F n is 6986, M w 15270, M w / M n The hydrocarbon copolymer F is soluble in toluene, xylene, tetrahydrofuran and dichloromethane (solid content above 50%), and no gel formation is observed.

[0053] Compared with Example 1, no 4-tert-butylstyrene was added to the reaction monomers in Comparative Example 2, and the yield of the polymer synthesized was lower.

[0054] The present invention successfully develops a divinylbenzene / styrene / 4-tert-butylstyrene terpolymer (PDVs) with controllable molecular weight and narrow molecular weight distribution synthesized by atom transfer radicals, and PDVs has excellent dielectric properties (dielectric constant: 2.29, dielectric loss tangent: 0.0036 at 10GHz), high heat resistance (Tg>175°C), low hygroscopicity (<0.2%) and other characteristics. The high-density benzene ring structure causes PDVs to crack easily during curing and has poor formability. Therefore, the present invention develops a series of hydrocarbon copolymers with self-toughening effect (such as Examples 2, 3, and 4) (PDVs-SBS) by directly adding styrene-butadiene-styrene copolymer (SBS) during polymerization, which improves the formability of PDVs. PDVs-SBS also has excellent heat resistance, water absorption and dielectric properties. The results show that hydrocarbon resins with self-toughening effect are more suitable for application in the fields of electronic packaging and high-performance printed circuit boards.

[0055] The test method in the present invention adopts the following standards:

[0056] Glass transition temperature T g: Measured by dynamic mechanical analyzer from room temperature to 300°C at 5°C / min.

[0057] Dielectric constant Dk and dielectric loss tangent tanδ: Data at 10 GHz were measured using Agilent PNA-N5234A from the United States.

[0058] The coefficient of linear thermal expansion (CTE) was measured using a thermomechanical analyzer at a rate of 10°C / min from room temperature to 300°C in a nitrogen atmosphere.

[0059] Thermal decomposition temperature: measured by thermogravimetric analysis at 10°C / min from room temperature to 600°C in a nitrogen atmosphere.

[0060] The technical contents not specifically described in the present invention and the above embodiments are the same as the prior art, and the raw materials are all commercially available products.

[0061] The present invention is not limited to the above embodiments, and all of the contents of the present invention can be implemented and have the above good effects.

Claims

1. A vinyl-containing hydrocarbon copolymer for high-frequency and high-speed copper-clad laminate and a preparation method thereof, characterized in that: The main chain of the vinyl-containing hydrocarbon copolymer has a plurality of terminal pendant double bonds; the vinyl-containing hydrocarbon copolymer is obtained by copolymerizing a divinyl aromatic compound, styrene and a monovinyl aromatic compound other than styrene; The divinyl aromatic compound is one of divinylbenzene, divinylnaphthalene and divinylbiphenyl, preferably divinylbenzene; the monovinyl aromatic compound other than styrene is one of 4-methylstyrene, 2,4-dimethylstyrene, ethylvinylbenzene and 4-tert-butylstyrene, preferably 4-tert-butylstyrene.

2. A self-toughening hydrocarbon copolymer for high-frequency and high-speed copper-clad laminate and a preparation method thereof, characterized in that: It comprises a vinyl hydrocarbon copolymer main chain and a hydrocarbon resin side chain; the vinyl hydrocarbon copolymer main chain has a plurality of terminal hanging double bonds; the vinyl hydrocarbon copolymer is copolymerized by divinyl aromatic compounds, styrene and monovinyl aromatic compounds other than styrene; the hydrocarbon resin side chain has a plurality of main chain double bonds and molecular side chain hanging double bonds; the hydrocarbon resin side chain is grafted to at least one of the plurality of terminal double bonds; The hydrocarbon resin side chain is one of hydrogenated styrene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, polystyrene butadiene copolymer, ethylene propylene diene monomer rubber or polybutadiene.

3. The method for preparing a vinyl-containing hydrocarbon copolymer according to claim 1, characterized in that: The following steps are involved: S1: Divinylbenzene, styrene, 4-tert-butylstyrene, ethyl 2-bromoisobutyrate, N,N,N',N',N''-pentamethyldiethylenetriamine, cupric bromide and xylene were placed in a three-necked flask and mixed evenly, and nitrogen was passed through for 20-30 minutes; cuprous bromide was added to the reaction system under a nitrogen atmosphere, and nitrogen was passed through for another 15-20 minutes; after the ventilation was completed, heating was performed to start the polymerization reaction. S2: Pour the reactant solution into a column filled with neutral alumina, remove impurities to obtain a clear reactant solution, gradually add the solution into 7-10 times of ice methanol solution to produce a white precipitate; filter and dry the white precipitate to obtain a vinyl-containing hydrocarbon copolymer; S3: Weigh the following raw materials in parts by weight: 100 parts of vinyl-containing hydrocarbon copolymer, 2 parts of di-tert-butyl peroxide isopropylbenzene, 10102 parts of antioxidant, and 100 parts of xylene; mix the above raw materials evenly to obtain a hydrocarbon resin glue; pour the glue into a tetrafluoroethylene mold, place it in an oven for heating and curing to obtain a finished product.

4. The method for preparing a self-toughening hydrocarbon copolymer according to claim 2, characterized in that: The following steps are involved: S1: Place hydrocarbon resin and xylene in a three-necked flask and stir until uniformly dispersed; then add divinylbenzene, styrene, 4-tert-butylstyrene, ethyl 2-bromoisobutyrate, N,N,N',N',N''-pentamethyldiethylenetriamine and cupric bromide, mix evenly, and pass nitrogen for 20-30 minutes. Add cuprous bromide to the reaction system under nitrogen atmosphere, and then pass nitrogen for 15-20 minutes; after the ventilation is completed, heat and start the polymerization reaction. S2: Pour the reactant solution into a column filled with neutral alumina, remove impurities to obtain a clear reactant solution, gradually add the solution into 7-10 times of ice methanol solution to produce a white precipitate; filter and dry the white precipitate to obtain a self-toughening hydrocarbon copolymer; S3: Weigh the following raw materials in parts by weight: 100 parts of a self-toughening hydrocarbon copolymer, 2 parts of di-tert-butyl peroxide isopropylbenzene, 2 parts of an antioxidant 1010, and 100 parts to 150 parts of xylene; mix the above raw materials evenly to obtain a hydrocarbon resin glue; pour the glue into a tetrafluoroethylene mold, place it in an oven to heat and cure it to obtain a finished product.

5. The method for preparing a vinyl-containing hydrocarbon copolymer according to claim 3, characterized in that: In step S1, the molar ratio of divinylbenzene: 4-tert-butylstyrene: styrene is 1:0~0.6:3.7; the molar ratio of the total mole of divinylbenzene, styrene and 4-tert-butylstyrene to ethyl 2-bromoisobutyrate, N,N,N',N',N''-pentamethyldiethylenetriamine, cupric bromide, cuprous bromide and xylene is 200:2:0.125:0.5:660; the heating temperature is 90°C and the reaction time is 24h.

6. The method for preparing a vinyl-containing hydrocarbon copolymer according to claim 3, characterized in that: In step S3, the curing program temperature is set to 80°C / 2h, 100°C / 2h, 120°C / 2h, 140°C / 2h, 160°C / 2h, and 180°C / 1h.

7. The method for preparing a self-toughening hydrocarbon copolymer according to claim 4, characterized in that: The hydrocarbon resin in step S1 is one of hydrogenated styrene-butadiene block copolymer, styrene-butadiene block copolymer, polystyrene butadiene copolymer, ethylene propylene diene monomer rubber or polybutadiene; the total mass ratio of the hydrocarbon resin to divinylbenzene, styrene and 4-tert-butylstyrene is 1:15-45, and the molar ratio of divinylbenzene, 4-tert-butylstyrene and styrene is 1:0.3:3; the molar ratio of the total mole of divinylbenzene, styrene and 4-tert-butylstyrene to ethyl 2-bromoisobutyrate, N,N,N',N',N''-pentamethyldiethylenetriamine, cupric bromide, cuprous bromide and xylene is 200:2:0.125:0.5:660; the heating temperature is 90°C and the reaction time is 24h.

8. The method for preparing a self-toughening hydrocarbon copolymer according to claim 4, characterized in that: In step S3, the curing program temperature is set to 80°C / 2h, 100°C / 2h, 120°C / 2h, 140°C / 2h, 160°C / 2h, and 180°C / 1h.

9. A preparation method of a vinyl-containing hydrocarbon resin and a self-toughening hydrocarbon resin as claimed in any one of claims 1 to 8 and their use in high-frequency and high-speed copper-clad laminates.