Bis(vinylbenzyl)fluorene and preparation method therefor and use thereof, and bis(vinylbenzyl)fluorene hydrocarbon resin and preparation method therefor and use thereof

Abstract

The present application relates to the technical field of high-frequency substrate materials, and provides bis(vinylbenzyl)fluorene and a preparation method therefor and the use thereof, and a bis(vinylbenzyl)fluorene hydrocarbon resin and a preparation method therefor and the use thereof. The bis(vinylbenzyl)fluorene hydrocarbon resin provided in the present application, which is prepared by using one of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene or a mixture of same at any ratio as a raw material, has a very low dielectric constant and dielectric loss tangent. Moreover, the higher the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene, the smaller the dielectric loss tangent of the bis(vinylbenzyl)fluorene hydrocarbon resin. Furthermore, 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided in the present application have high solubility in toluene and 2-butanone, and have good application prospects as main resins for high-frequency substrates or as cross-linking agents for alkenyl resin components.

Description

A divinylbenzylfluorene, a preparation method and application thereof, and a divinylbenzylfluorene hydrocarbon resin, a preparation method and application thereof

[0001] The present application claims priority to the Chinese patent application No. CN202411095175.5, filed on August 9, 2024, and entitled "A divinylbenzylfluorene, a preparation method and application thereof, and a divinylbenzylfluorene hydrocarbon resin, a preparation method and application thereof", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present application relates to the technical field of high-frequency substrate materials, in particular to a divinylbenzylfluorene, a preparation method and application thereof, and a divinylbenzylfluorene hydrocarbon resin, a preparation method and application thereof. BACKGROUND

[0003] Low dielectric constant (D k ) and low dielectric loss tangent (D f ) resin is a key material in the field of microelectronics such as high-frequency substrates, antennas, etc. Modified polyphenylene oxide (MPPO) terminated by vinylbenzyl or acryloyl groups has a relatively low dielectric constant and dielectric loss tangent, and is widely used as a laminated board material for printed circuit boards (PCB). However, with the rapid development of 5G / 6G communication, AR / VR and artificial intelligence, electronic products tend to require higher transmission speed, frequency and greater capacity to transmit sound, video and data. At the same time, electronic products tend to develop in the direction of light, thin and small. In order to maintain high transmission rate and signal integrity, the core component of electronic products, printed circuit boards, need to have resin materials with lower dielectric constant and lower dielectric loss tangent. Therefore, further reducing the dielectric constant and dielectric loss of resin materials is a key technical problem to be solved at present.

[0004] 9,9-disubstituted fluorenyl hydrocarbon derivatives have good photoelectric properties such as low dielectric constant, high refractive index and transparency, as well as good heat resistance, moisture resistance and good solubility in organic solvents, due to their unique Cardo structure, and are widely used as microelectronic device materials.

[0005] JP2003283076A discloses a mixture prepared by reacting vinylbenzyl chloride and allyl chloride with fluorene, the dielectric constant (5 GHz) of the thermosetting resin thereof is 4.0, the dielectric loss tangent (5 GHz) thereof is 0.0035, and the vinylbenzyl chloride thereof is a mixture of meta and para isomers in a mass ratio of 1:1. CN1501899A and US7514379B2 disclose a mixture of meta and para isomers of 9,9-bis(vinylbenzyl)-9H-fluorene with a melting point of 142℃, which is prepared by reacting vinylbenzyl chloride and allyl chloride with fluorene, the dielectric constant (1 MHz) of the thermosetting resin thereof is 2.65, the dielectric loss tangent (1 MHz) thereof is 0.0013, and the vinylbenzyl chloride thereof is a mixture of meta and para isomers in a mass ratio of 1:1. WO2022207741A1 discloses that the dielectric constant (10 GHz) of the thermosetting laminate of the combined material of vinylbenzyl indene and a mixture of 9,9-bis(vinylbenzyl)-9H-fluorene containing meta isomers and bismaleimide is 2.55, and the dielectric loss tangent (10 GHz) thereof is 0.00089. However, the above-mentioned 9,9-disubstituted fluorenyl hydrocarbon derivatives do not obtain a single isomer, and are all mixtures containing meta isomers (9,9-bis(3-vinylbenzyl)-9H-fluorene), and due to the high melting point and poor solubility in organic solvents and poor compatibility with alkenyl resins of the meta isomer of the 9,9-disubstituted fluorenyl hydrocarbon derivatives, the dielectric loss tangent of the thermosetting resin is not low enough.

[0006] SUMMARY

[0007] Therefore, the purpose of the present application is to provide a kind of double vinylbenzyl fluorene and its preparation method and application, double vinylbenzyl fluorene carbon hydrogen resin without meta isomer and its preparation method and application.The double vinylbenzyl fluorene provided by the present application has high purity and does not contain meta isomer, and the dielectric loss tangent of the double vinylbenzyl fluorene carbon hydrogen resin prepared from the double vinylbenzyl fluorene is small, and the dielectric constant is low.

[0008] In order to achieve the above-mentioned purpose of the application, the following technical solutions are provided:

[0009] The present application provides a kind of double vinylbenzyl fluorene, which is 9,9-bis(2-vinylbenzyl)-9H-fluorene (9,9-bis(2-vinylbenzyl)-9H-fluorene, abbreviated as o,o-BVBF) with the structure shown in formula I or 9,9-bis(4-vinylbenzyl)-9H-fluorene (9,9-bis(4-vinylbenzyl)-9H-fluorene, abbreviated as p,p-BVBF) with the structure shown in formula II:

[0010] The 9,9-bis(2-vinylbenzyl)-9H-fluorene has monoclinic system;

[0011] The 9,9-bis(4-vinylbenzyl)-9H-fluorene has triclinic system.

[0012] The application further provides a preparation method of the above-mentioned double vinyl benzyl fluorene, comprising the following steps:

[0013] The fluorene, vinyl benzyl chloride, alkaline reagent, polymerization inhibitor, phase transfer catalyst and solvent are mixed to perform a phase transfer reaction to obtain the double vinyl benzyl fluorene; the vinyl benzyl chloride is 2-vinyl benzyl chloride or 4-vinyl benzyl chloride.

[0014] Preferably, the phase transfer catalyst comprises one or more of quaternary ammonium salt, quaternary phosphonium salt and polyethylene glycol; the mass of the phase transfer catalyst is 10-35% of the mass of the fluorene;

[0015] The organic solvent comprises one or more of aromatic hydrocarbon, aliphatic hydrocarbon, petroleum ether and acetonitrile.

[0016] Preferably, the temperature of the phase transfer reaction is 25-45℃, the time is 12-18h, and the phase transfer reaction is performed under stirring.

[0017] Preferably, the polymerization inhibitor comprises one or more of nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, o-benzoquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine N-oxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine N-oxide;

[0018] The mass of the polymerization inhibitor is 0.01-0.5% of the mass of the vinyl benzyl chloride.

[0019] Preferably, the molar ratio of the fluorene and vinyl benzyl chloride is 1:2-2.5.

[0020] The application further provides a double vinyl benzyl fluorene hydrocarbon resin, and the preparation raw material comprises double vinyl benzyl fluorene, the double vinyl benzyl fluorene is 9,9-bis(2-vinylbenzyl)-9H-fluorene having the structure shown in formula I and / or 9,9-bis(4-vinylbenzyl)-9H-fluorene having the structure shown in formula II:

[0021] Preferably, when the double vinyl benzyl fluorene is a mixture of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene, the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene in the mixture is ≥5wt%.

[0022] The application further provides a preparation method of the divinylbenzylfluorene hydrogen carbon resin in the technical solution.

[0023] The application further provides application of the divinylbenzylfluorene hydrogen carbon resin in the technical solution or the divinylbenzylfluorene hydrogen carbon resin prepared by the preparation method in the technical solution in a high-frequency substrate.

[0024] 9,9-Divinylbenzyl-9H-fluorene has multiple isomers, and the geometric characteristics and crystal forms of divinylbenzylfluorene isomers with different structures can affect the dielectric constant, dielectric loss tangent and solubility in organic solvents and other physical properties. The divinylbenzylfluorene provided in the application has a purity higher than 99%, is high in purity and free of meta isomers (9,9-bis(3-vinylbenzyl)-9H-fluorene shown in formula III and 9-(3-vinylbenzyl)-9-(4-vinylbenzyl)-9H-fluorene shown in formula IV).

[0025] The 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided in the application can be dissolved in toluene and / or 2-butanone at room temperature (25°C) to form transparent solutions, and are suitable for use as crosslinking agents of alkenyl resin components of high-frequency substrates. The divinylbenzylfluorene hydrogen carbon resin prepared from the 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided in the application both have low dielectric constants and low dielectric loss tangents.

[0026] As shown in the test results of the examples, the dielectric constant D k (10 GHz) of the divinylbenzylfluorene hydrogen carbon resin prepared from 9,9-bis(2-vinylbenzyl)-9H-fluorene is 2.8, and the dielectric loss tangent D f (10 GHz) is 0.00032; the dielectric constant D k (10 GHz) of the divinylbenzylfluorene hydrogen carbon resin prepared from 9,9-bis(4-vinylbenzyl)-9H-fluorene is 2.8, and the dielectric loss tangent D f (10 GHz) is 0.00047. The divinylbenzylfluorene hydrogen carbon resin has a low dielectric constant and a small dielectric loss tangent.

[0027] The mixture of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene in any ratio prepared by using the mixture as raw material has low dielectric constant and low dielectric loss tangent, and the higher the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene, the smaller the dielectric loss tangent of the divinylbenzyl fluorene hydrocarbon resin. When the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene is ≥20wt%, the dielectric loss tangent of the divinylbenzyl fluorene hydrocarbon resin is ≤0.00044.

[0028] Compared with 1,2-bis(4-vinylphenyl)ethane resin, the mixture of meta and para isomers of 9,9-bis(vinylbenzyl)-9H-fluorene, and the mixture of ortho, meta and para isomers of 9,9-bis(vinylbenzyl)-9H-fluorene, the dielectric loss tangent of the divinylbenzyl fluorene hydrocarbon resin prepared by using one or both of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided by the application as raw material is significantly reduced, and the solubility of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided by the application in toluene or 2-butanone is significantly improved compared with 1,2-bis(4-vinylphenyl)ethane or meta isomer 9,9-bis(vinylbenzyl)-9H-fluorene, and the divinylbenzyl fluorene hydrocarbon resin provided by the application has good application prospect as the main resin of high-frequency substrate.

[0029] The preparation method of the divinylbenzyl fluorene provided by the application can obtain single isomers (9,9-bis(2-vinylbenzyl)-9H-fluorene, 9,9-bis(4-vinylbenzyl)-9H-fluorene), the compound has high purity, the process is simple, the operation is simple, the cost is low, and the method is suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is an HPLC chart of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0031] Figure 2 is a 1 H NMR chart of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0032] Figure 3 is a DQF-COSY 1 H- 1 H correlation nuclear magnetic resonance spectrum two-dimensional chart of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0033] Figure 4 is a 13 C NMR chart of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0034] Figure 5 is an FT-IR spectrum of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0035] Figure 6 is a thermal analysis DSC spectrum of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0036] Figure 7 is a single crystal structure of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0037] Figure 8 is a unit cell packing diagram of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0038] Figure 9 is an X-ray powder diffraction spectrum of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1;

[0039] Figure 10 is an HPLC chart of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3;

[0040] Figure 11 is a H NMR chart of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3; 1

[0041] Figure 12 is a CNMR chart of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3; 13

[0042] Figure 13 is a thermal analysis DSC spectrum of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3;

[0043] Figure 14 is an FT-IR spectrum of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3;

[0044] Figure 15 is a single crystal structure of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3;

[0045] Figure 16 is a unit cell packing diagram of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3;

[0046] Figure 17 is an X-ray powder diffraction spectrum of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3. DETAILED DESCRIPTION

[0047] The present application provides a divinylbenzylfluorene, which is 9,9-bis(2-vinylbenzyl)-9H-fluorene having a structure shown in Formula I or 9,9-bis(4-vinylbenzyl)-9H-fluorene having a structure shown in Formula II: ​​

[0048] In the present application, the 9,9-bis(2-vinylbenzyl)-9H-fluorene (crystal) has monoclinic system; the X-ray powder diffraction analysis characteristic peak 2Θ of the 9,9-bis(2-vinylbenzyl)-9H-fluorene preferably includes: 11.9°, 12.3°, 14.2°, 15.4°, 18.5°, 19.2°, 20.0°, 20.7°, 22.2°, 23.7° and 24.7°; the melting point of the 9,9-bis(2-vinylbenzyl)-9H-fluorene is preferably 124-126°C, more preferably 124.0-125.5°C; the purity of the 9,9-bis(2-vinylbenzyl)-9H-fluorene is preferably >99.0%; the space group of the 9,9-bis(2-vinylbenzyl)-9H-fluorene is preferably P21 / c; the unit cell parameters are preferably α = 90°, β = 96.243(2)°, γ = 90°.

[0049] In the present application, the 9,9-bis(4-vinylbenzyl)-9H-fluorene (crystal) has triclinic system; the X-ray powder diffraction analysis characteristic peak 2Θ of the 9,9-bis(4-vinylbenzyl)-9H-fluorene preferably includes: 11.1°, 12.0°, 18.6°, 19.1°, 20.0°, 22.1°, 23.6°, 24.0° and 24.6°; the melting point of the 9,9-bis(4-vinylbenzyl)-9H-fluorene is preferably 118-120°C, more preferably 118.4-119.8°C; the purity of the 9,9-bis(4-vinylbenzyl)-9H-fluorene is preferably >99.0%; the space group of the 9,9-bis(4-vinylbenzyl)-9H-fluorene is the unit cell parameters are α = 94.299(2)°, β = 92.157(2)°, γ = 91.265(3)°.

[0050] The mixture of one or both of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene in any ratio provided in the application is used as raw material to prepare the divinylbenzyl fluorene hydrocarbon resin, which has very low dielectric constant and dielectric loss tangent, and the higher the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene, the smaller the dielectric loss tangent of the divinylbenzyl fluorene hydrocarbon resin; and the solubility of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene in toluene and 2-butanone is high. The mixture of one or both of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene in any ratio also has a good application prospect as a crosslinking agent of alkenyl resin component. The divinylbenzyl fluorene hydrocarbon resin prepared from the mixture of one or both of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene has a good application prospect as a main resin of high-frequency substrate.

[0051] The application provides a preparation method of the divinylbenzyl fluorene, which comprises the following steps: mixing fluorene, vinylbenzyl chloride, an alkaline reagent, a polymerization inhibitor, a phase transfer catalyst and an organic solvent to perform a phase transfer reaction to obtain the divinylbenzyl fluorene; the vinylbenzyl chloride is 2-vinylbenzyl chloride or 4-vinylbenzyl chloride.

[0052] Unless otherwise specified, the materials and equipment used in the application are commercially available in the art.

[0053] In the application, the molar ratio of the fluorene and the vinylbenzyl chloride is preferably 1:2-2.5, more preferably 1:2.1-2.4, and further preferably 1:2.2-2.3. In the application, the 2-vinylbenzyl chloride (CAS: 22570-84-9) and the 4-vinylbenzyl chloride (CAS: 1592-20-7) are both produced by Shandong Xingshun New Material Co., Ltd.; the purity of the 2-vinylbenzyl chloride is preferably 99.0%, and the purity of the 4-vinylbenzyl chloride is preferably 99.5%.

[0054] In the application, the alkaline reagent preferably includes an alkali metal hydroxide and / or an alkali metal alcoholate; the alkali metal hydroxide preferably includes one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and more preferably potassium hydroxide; the alkali metal alcoholate preferably includes one or more of sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, sodium isopropoxide, potassium isopropoxide, sodium tert-butoxide and potassium tert-butoxide, and more preferably potassium tert-butoxide. In the application, the molar ratio of the fluorene and the alkaline reagent is preferably 1:1.8-5, more preferably 1:2-4, and most preferably 1:2-3.

[0055] In the present application, the polymerization inhibitor preferably comprises one or more of nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine-N-oxyl and 2,2,6,6-tetramethyl-4-hydroxypiperidine-N-oxyl (polymerization inhibitor 701). In the present application, the mass of the polymerization inhibitor is preferably 0.01-0.5% of the mass of the vinylbenzyl chloride, more preferably 0.1-0.4%, and most preferably 0.2-0.3%.

[0056] In the present application, the phase transfer catalyst preferably comprises one or more of quaternary ammonium salt, quaternary phosphonium salt and polyethylene glycol (PEG), and more preferably polyethylene glycol; the number average molecular weight of the polyethylene glycol is preferably 200-600, and more preferably 400-600; and the polyethylene glycol particularly preferably comprises one or more of PEG-200, PEG-400 and PEG-600. In the present application, the mass of the phase transfer catalyst is preferably 10-35% of the mass of the fluorene, and more preferably 20-30%.

[0057] In the present application, the organic solvent preferably comprises one or more of aromatic hydrocarbon, aliphatic hydrocarbon, petroleum ether and acetonitrile, and more preferably aromatic hydrocarbon or acetonitrile; the aromatic hydrocarbon preferably comprises one or more of toluene, xylene and ethylbenzene, and more preferably toluene; and the aliphatic hydrocarbon preferably comprises one or more of cyclohexane, n-hexane and n-heptane. In the present application, the ratio of the mass of the fluorene to the volume of the organic solvent is preferably 1 g: 3-8 mL, and more preferably 1 g: 5 mL.

[0058] In the present application, the temperature of the phase transfer reaction is preferably 25-45°C, more preferably 30-40°C, and further preferably 30-35°C; the time of the phase transfer reaction is preferably 12-18 h, more preferably 13-16 h, and further preferably 14-15 h; and the phase transfer reaction is preferably carried out under stirring, and the stirring speed is preferably 200-500 r / min, and more preferably 300-400 r / min. In the specific embodiments of the present application, the phase transfer reaction is stopped when the content of fluorene in the reaction system is <1 wt%.

[0059] After the phase transfer reaction is completed, the present application preferably further comprises post-treatment, which preferably comprises: subjecting the reaction system obtained from the phase transfer reaction to first concentration, adding water and toluene to separate into layers, subjecting the obtained organic phase to washing with saturated ammonium chloride solution, washing with water until neutral, second concentration, recrystallization and solid-liquid separation, drying the obtained solid component, to obtain the divinylbenzylfluorene.

[0060] The first concentration and the second concentration are not particularly limited in the present application, and any concentration method known to those skilled in the art can be used, for example, evaporation or reduced pressure distillation.

[0061] In the present application, the solvent used in the recrystallization preferably includes one or more of aromatic hydrocarbon solvents, ketone solvents, ether solvents, alcohol solvents and acetonitrile; the aromatic hydrocarbon solvents preferably include one or more of toluene, xylene, ethylbenzene and cumene; the ketone solvents preferably include one or more of acetone, 2-butanone and methyl isobutyl ketone; the ether solvents preferably include one or more of methyl tert-butyl ether, tetrahydrofuran, methyl tetrahydrofuran and anisole; the alcohol solvents preferably include one or more of methanol, ethanol and isopropanol; the solvent used in the recrystallization more preferably is a toluene-methanol mixed solvent or a toluene-acetonitrile mixed solvent; the volume ratio of toluene to methanol in the toluene-methanol mixed solvent preferably is 1:0.1-0.6, more preferably 1:0.2-0.4; the volume ratio of toluene to acetonitrile in the toluene-acetonitrile mixed solvent preferably is 1:0.1-0.6, more preferably 1:0.2-0.4. In the present application, the recrystallization preferably includes heating to complete dissolution and then cooling to -10-20°C for isothermal crystallization; the cooling rate of the cooling preferably is 0.2-1°C / min, more preferably 0.4-0.5°C / min; the temperature of the isothermal crystallization more preferably is 5-10°C.

[0062] The solid-liquid separation is not particularly limited in the present application, and any solid-liquid separation method known to those skilled in the art can be used, for example, filtration, suction filtration or centrifugal separation.

[0063] In the present application, the drying temperature preferably is 70-110°C, more preferably 80-90°C; the drying time is not particularly limited in the present application, and the drying can be performed until a constant weight is obtained.

[0064] The present application also provides the use of the divinylbenzylfluorene prepared by the preparation method described in the above technical solution or the divinylbenzylfluorene described in the above technical solution in high-frequency substrates. In the present application, the use preferably is the use as a crosslinking agent for high-frequency substrates; the crosslinking agent preferably is a crosslinking agent for alkenyl resin components, and the alkenyl resin components preferably include terminal-vinyl-modified polyphenylene ethers. In the present application, the divinylbenzylfluorene is preferably used as a crosslinking agent for high-frequency substrates; the divinylbenzylfluorene hydrocarbon resin is preferably used as a main resin for high-frequency substrates. The 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene and any proportion of mixtures provided by the present application can be dissolved in toluene and 2-butanone in a mass ratio of 1:1 to form a transparent solution, have high solubility in toluene and 2-butanone, and have good application prospects as crosslinking agents for alkenyl resin components of high-frequency substrates.

[0065] The present application also provides a divinylbenzylfluorene hydrocarbon resin, raw materials for preparation of which include divinylbenzylfluorene, the divinylbenzylfluorene being 9,9-bis(2-vinylbenzyl)-9H-fluorene having the structure shown in Formula I and / or 9,9-bis(4-vinylbenzyl)-9H-fluorene having the structure shown in Formula II:

[0066] In the present application, when the divinylbenzylfluorene is a mixture of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene, the present application does not have special limitations on the mass ratio of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene in the mixture, and any ratio can be used. Specifically, the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene in the mixture is preferably ≥ 5 wt%, more preferably ≥ 10 wt%, and specifically preferably 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt% or 95 wt%. In the present application, the higher the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene in the mixture, the lower the dielectric loss tangent of the divinylbenzylfluorene hydrocarbon resin, and when the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene is > 20 wt%, the D k (10 GHz) is 2.8, and D f (10 GHz) < 0.00044.

[0067] The present application also provides a preparation method of the divinylbenzylfluorene hydrocarbon resin described in the above technical solution, which comprises the following steps: subjecting divinylbenzylfluorene to thermal curing to obtain the divinylbenzylfluorene hydrocarbon resin.

[0068] In the present application, the thermal curing preferably comprises melt sample casting. In the present application, the temperature of the thermal curing is preferably 200°C, the pressure is preferably 70-80 mmHg, and the time is preferably 30 min.

[0069] The application also provides the use of the divinylbenzylfluorene described in the technical solution, the divinylbenzylfluorene prepared by the preparation method described in the technical solution, the divinylbenzylfluorene hydrocarbon resin described in the technical solution or the divinylbenzylfluorene hydrocarbon resin prepared by the preparation method described in the technical solution in high-frequency substrates. In the application, the use is preferably the use as a main resin or a crosslinking agent of a high-frequency substrate; the crosslinking agent is preferably a crosslinking agent of an alkenyl resin component, and the alkenyl resin component preferably comprises a terminal-vinyl-modified polyphenylene ether. In the application, the divinylbenzylfluorene is preferably used as a crosslinking agent of a high-frequency substrate; and the divinylbenzylfluorene hydrocarbon resin is preferably used as a main resin of a high-frequency substrate.

[0070] The divinylbenzylfluorene hydrocarbon resin prepared by using one of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene or a mixture thereof in any ratio as a raw material has very low dielectric constant and dielectric loss tangent, and the higher the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene, the smaller the dielectric loss tangent of the divinylbenzylfluorene hydrocarbon resin; and the 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene and the mixture thereof in any ratio provided by the application can be dissolved in toluene and 2-butanone to form a transparent solution according to a mass ratio of 1:1 of the compound to the solvent, and has high solubility in toluene and 2-butanone. The divinylbenzylfluorene hydrocarbon resin has a good application prospect as a main resin of a high-frequency substrate.

[0071] In order to further illustrate the application, one of the divinylbenzylfluorene, the preparation method and the use thereof, the divinylbenzylfluorene hydrocarbon resin and the preparation method and the use thereof provided by the application are described in detail below in combination with examples, but they should not be understood as limiting the protection scope of the application.

[0072] In the following examples, 2-vinylbenzyl chloride (HPLC purity of 99.0%, produced by Shandong Xingshun New Material Co., Ltd.) and 4-vinylbenzyl chloride (HPLC purity of 99.5%, produced by Shandong Xingshun New Material Co., Ltd.).

[0073] The analysis instruments and analysis test methods used are as follows:

[0074] 1. Purity determination method (HPLC): American Agillent 1260 high-pressure liquid chromatograph; column type: Kromasil 100-5 C18 250 cm x 4.6 mm; mobile phase: acetonitrile / methanol volume ratio = 9:1; flow rate: 0.8 mL / min; detection wavelength: 254 nm; injection amount: 2 μL; pump mode: binary high-pressure gradient.

[0075] 2. Thermal analysis method: DSC was measured by Pyris 1 thermal analyzer (Perkin Elemer), heating range 50-200℃, heating rate 10℃ / min.

[0076] 3. Nuclear magnetic resonance spectrum measurement: Bruker AV 400 nuclear magnetic resonance instrument, DMSO-d6 as solvent, TMS as internal standard.

[0077] 4. Infrared spectrum measurement: NEXUS 870 Fourier transform infrared spectrum (FT-IR) instrument (NICOLET), potassium bromide tabletting.

[0078] 5. Single crystal structure measurement: Bruker D8 Venture single crystal diffractometer, JY / T 0588-2020 general method for molecular structure analysis.

[0079] 6. Dielectric constant D k (10GHz) and dielectric loss tangent D f (10GHz) measurement: melt sample casting method (thermal curing conditions: temperature 200℃, pressure 70-80mmHg, time 30min) was used to make 80mm×80mm×0.4mm resin sheet, and American Agilent N5230A type vector network analyzer was used to measure at frequency 10GHz.

[0080] 7. X-ray powder diffraction spectrum measurement: Bruker D2 Phaser polycrystalline diffractometer, JY / T 0587-2020 general method for analysis.

[0081] Example 1

[0082] In a reaction flask, 500 mL of acetonitrile, 1.4 mol of potassium hydroxide powder, 30 g of PEG-400, 0.5 g of polymerization inhibitor 701, 0.6 mol of fluorene, and 1.4 mol of 2-vinylbenzyl chloride (HPLC, 99%) were added under stirring. The reaction was carried out at 30-35°C and 350 r / min until the content of fluorene was less than 1 wt% by HPLC analysis. The reaction was stopped, and after the acetonitrile was evaporated, 500 mL of water and 500 mL of toluene were added, the organic phase was washed with saturated ammonium chloride solution, and washed with water three times (500 mL of water each time) until it was neutral. The toluene was evaporated under reduced pressure, a mixed solvent of toluene and methanol with a volume ratio of 1:0.3 was added, and the mixture was heated to complete dissolution. The temperature was decreased to 5°C at a rate of 0.5°C / min, and the mixture was kept at this temperature for crystallization. The solid component was filtered and dried at 90°C until the weight was constant, obtaining 191.5 g of 9,9-bis(2-vinylbenzyl)-9H-fluorene, o,o-BVBF, white crystals, with a purity of 99.4% by HPLC (Figure 1 and Table 1), a melting point (DSC melting absorption peak, Figure 6) of 124.0-125.5°C, and a yield of 80.1%.

[0083] Table 1 HPLC peak information of o,o-BVBF

[0084] Figure 2 is a 1H NMR spectrum of o,o-BVBF, Figure 3 is a DQF-COSY 2D NMR spectrum of o,o-BVBF, 1 1 1 13 Figure 4 is a13C NMR spectrum of o,o-BVBF, and Figure 5 is a FT-IR spectrum of o,o-BVBF. 1 H NMR (400 MHz, DMSO-d6) δ: 3.54 (s, 4H, 2xCH2), 5.10 (d, 2H, 2xterminal vinyl hydrogen), 5.42 (d, 2H, 2xterminal vinyl hydrogen), 6,54 (d, 2H, 2xphenyl hydrogen), 6.79-6.87 (m, 4H, 2xphenyl hydrogen, 2xCH=CH2), 6.97-7.01 (m, 2H, 2xphenyl hydrogen), 7.15-7.19 (m, 2H, 2xfluorene ring hydrogen), 7.22-7.24 (m, 2H, 2xphenyl hydrogen), 7.25-7.29 (m, 2H, 2xfluorene ring hydrogen), 7.40 (d, 2H, 2xfluorene ring hydrogen), 7.60 (d, 2H, 2xfluorene ring hydrogen). 13 ​​​C NMR (100 MHz, DMSO-d6) δ: 40.1 (CH2), 56.3 (9-fluorene C), 115.1, 119.7, 125.1, 125.2, 126.2, 126.3, 126.4, 127.1, 130.2, 135.0, 135.1, 136.9, 140.1, 148.4 (benzene ring C, fluorene ring C, vinyl C).

[0085] Figure 7 is a single crystal structure diagram of o,o-BVBF, Figure 8 is a unit cell packing diagram of o,o-BVBF, and Figure 9 is an X-ray powder diffraction spectrum of o,o-BVBF. The crystallographic parameters of o,o-BVBF are shown in Tables 2-5. It can be seen that the single crystal structure of o,o-BVBF is determined to be a white monoclinic crystal, and the characteristic peak 2θ (relative intensity %) of the X-ray powder diffraction analysis is 11.9 (70), 12.3 (20), 14.2 (20), 15.4 (30), 18.5 (76), 19.2 (44), 20.0 (47), 20.7 (100), 22.2 (21), 23.7 (100), 24.7 (30).

[0086] Table 2 Crystallographic table of o,o-BVBF and p,p-BVBF

[0087] Table 3 Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters of o,o-BVBF

[0088] Table 4 Bond lengths and bond angles [°] of o,o-BVBF

[0089] Table 5 Anisotropic displacement parameters of o,o-BVBF

[0090] Example 2

[0091] In a reaction flask, 350 mL of acetonitrile, 1.4 mol of potassium hydroxide powder, 30 g of PEG-400, and 0.5 g of polymerization inhibitor 701 were added, and 0.6 mol of fluorene and 1.4 mol of 4-vinylbenzyl chloride (HPLC 99.5%) were added under stirring. The reaction was carried out at 30-35°C under stirring at 350 r / min until the content of fluorene was less than 1 wt% as analyzed by HPLC. The reaction was stopped, and after the acetonitrile was evaporated, 500 mL of water and 500 mL of toluene were added, and the organic phase was separated. The obtained organic phase was washed with saturated ammonium chloride solution and water three times (500 mL of water each time) until it was neutral. The toluene was evaporated under reduced pressure, and a mixed solvent of toluene and methanol (volume ratio 1:0.3) was added. The mixture was heated to complete dissolution, and the temperature was decreased to 5°C at a rate of 0.5°C / min. The obtained solid component was dried at 90°C until the weight was constant, and 197.6 g of 9,9-bis(4-vinylbenzyl)-9H-fluorene, p,p-BVBF, white crystal, was obtained. The HPLC purity (Fig. 10 and Table 6) was 99.7%, the melting point was 118.4-119.8°C (thermal analysis DSC melting absorption peak, Fig. 13), and the yield was 82.6%.

[0092] Example 3

[0093] In a reaction flask, 350 mL of acetonitrile, 1.4 mol of potassium hydroxide powder, 30 g of PEG-400, and 0.5 g of polymerization inhibitor 701 were added, and 0.6 mol of fluorene and 1.4 mol of 4-vinylbenzyl chloride (HPLC 99.5%) were added under stirring. The reaction was carried out at 30-35°C under stirring at 350 r / min until the content of fluorene was less than 1 wt% as analyzed by HPLC. The reaction was stopped, and after the acetonitrile was evaporated, 500 mL of water and 500 mL of toluene were added, and the organic phase was separated. The obtained organic phase was washed with saturated ammonium chloride solution and water three times (500 mL of water each time) until it was neutral. The toluene was evaporated under reduced pressure, and a mixed solvent of toluene and methanol (volume ratio 1:0.3) was added. The mixture was heated to complete dissolution, and the temperature was decreased to 5°C at a rate of 0.5°C / min. The obtained solid component was dried at 90°C until the weight was constant, and 197.6 g of 9,9-bis(4-vinylbenzyl)-9H-fluorene, p,p-BVBF, white crystal, was obtained. The HPLC purity (Fig. 10 and Table 6) was 99.7%, the melting point was 118.4-119.8°C (thermal analysis DSC melting absorption peak, Fig. 13), and the yield was 82.6%.

[0094] Table 6 HPLC peak information of p,p-BVBF

[0095] Fig. 11 is an H NMR spectrum of p,p-BVBF, Fig. 12 is a C NMR spectrum of p,p-BVBF, and Fig. 14 is an FT-IR spectrum of p,p-BVBF. 1 Fig. 11 is an H NMR spectrum of p,p-BVBF, Fig. 12 is a C NMR spectrum of p,p-BVBF, and Fig. 14 is an FT-IR spectrum of p,p-BVBF. 13 Fig. 11 is an H NMR spectrum of p,p-BVBF, Fig. 12 is a C NMR spectrum of p,p-BVBF, and Fig. 14 is an FT-IR spectrum of p,p-BVBF. 1H NMR (400 MHz, DMSO-d6) δ: 3.48 (s, 4H, 2 x CH2), 5.08 (d, 2H, 2 x vinylic H), 5.61 (d, 2H, 2 x vinylic H), 6.45-6.52 (m, 2H, 2 x CH=CH2), 6,57 (d, 4H, 4 x phenyl H), 6.96 (d, 4H, 4 x phenyl H), 7.20-7.24 (m, 2H, 2 x fluorene H), 7.34-7.37 (m, 2H, 2 x fluorene H), 7.47 (d, 2H, 2 x fluorene H), 7.77 (d, 2H, 2 x fluorene H). 13 C NMR (100 MHz, DMSO-d6) δ: 44.5 (CH2), 56.9 (9-fluorene C), 113.2, 119.7, 124.6, 124.8, 126.4, 126.9, 129.9, 134.4, 136.3, 136.9, 140.5, 147.7 (phenyl C, fluorene C, vinylic C).

[0096] Figure 15 is a single crystal structure diagram of p,p-BVBF, Figure 16 is a unit cell packing diagram of p,p-BVBF, and Figure 17 is an X-ray powder diffraction spectrum of p,p-BVBF. The crystallographic parameters of p,p-BVBF are shown in Table 2 and Tables 7-9. It can be seen that the single crystal of p,p-BVBF is white and crystallizes in triclinic system. The characteristic peaks 2Θ (relative intensity %) of X-ray powder diffraction analysis of p,p-BVBF are 11.1 (100), 12.0 (43), 18.6 (64), 19.1 (30), 20.0 (36), 22.1 (29), 23.6 (25), 24.0 (39), 24.6 (26).

[0097] Table 7 Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters of p,p-BVBF

[0098] Table 8 Bond lengths and bond angles [°] of p,p-BVBF

[0099] Table 9 Anisotropic displacement parameters of p,p-BVBF

[0100] Example 4

[0101] Add 350 mL of acetonitrile, 1.4 mol of potassium tert-butoxide, 30 g of PEG-400, and 0.5 g of polymerization inhibitor 701 to the reaction flask. Under stirring conditions, add 0.6 mol of fluorene and 1.4 mol of 4-vinylbenzyl chloride (HPLC 99.5%). The reaction was carried out at 30–35 °C and 350 r / min with stirring until the fluorene content was <1 wt% according to HPLC analysis. The reaction was then stopped, acetonitrile was evaporated, and 500 mL of water and 500 mL of toluene were added to separate the phases. The resulting organic phase was washed with saturated ammonium chloride solution and water three times (500 mL each time) until neutral. Toluene was evaporated under reduced pressure, and the solid was heated to dissolve completely with a toluene-methanol mixture of volume ratio 1:0.3. The solid was then cooled to 5 °C at a rate of 0.5 °C / min and kept at a constant temperature to crystallize. The solid was filtered and dried at 90 °C to constant weight to obtain 202.3 g of 9,9-bis(4-vinylbenzyl)-9H-fluorene, white crystals with an HPLC purity of 99.5% and a yield of 84.5%.

[0102] The proton NMR spectrum of the synthesized divinylbenzylfluorene product of this application ( 1 H NMR, carbon spectrum 13 The NMR (1H NMR) and FT-IR spectra of divinylbenzylfluorene are in perfect agreement with the structures of the two isomers, 9,9-bis(2-vinylbenzyl)-9H-fluorene (o,o-BVBF) and 9,9-bis(4-vinylbenzyl)-9H-fluorene (p,p-BVBF), respectively. The assignment of peaks in the 1H NMR spectrum of o,o-BVBF is determined by DQF-COSY. 1 H- 1 The two-dimensional NMR spectrum of H-correlation was used to determine the structure of the product obtained by recrystallization from a toluene-methanol (volume ratio = 1:1) mixed solvent using a Bruker D8 Venture single-crystal diffractometer, further confirming that the single isomers 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene were successfully prepared in this application.

[0103] 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene or a mixture of the two in any ratio can be completely dissolved in toluene and 2-butanone at room temperature (25°C) to form clear transparent solutions. The mass ratio of bisvinylbenzylfluorene to toluene is 1:1, and the mass ratio of bisvinylbenzylfluorene to 2-butanone is 1:1. The crosslinking agent commonly used in printed circuit board resins, 1,2-bis(4-vinylphenyl)ethane (BVPE, CAS: 48174-52-3) and the meta-containing bisvinylbenzylfluorene isomers in the comparative examples have only 20% solubility in toluene or 2-butanone, indicating that the solubility of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in the present application in organic solvents is much greater than that of 1,2-bis(4-vinylphenyl)ethane and meta-bisvinylbenzylfluorene isomers.

[0104] Example 5

[0105] The 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 was made into a 80mmx80mmx0.4mm resin sheet by melt casting (thermal curing conditions: temperature 200°C, pressure 70-80mmHg, time 30min), and the dielectric constant and dielectric loss tangent of the sample at a frequency of 10GHz were measured using an Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0106] Example 6

[0107] The 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 was made into a 80mmx80mmx0.4mm resin sheet by melt casting (thermal curing conditions: temperature 200°C, pressure 70-80mmHg, time 30min), and the dielectric constant and dielectric loss tangent of the sample at a frequency of 10GHz were measured using an Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0108] Example 7

[0109] The 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 and the 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 were mixed in a weight ratio of 20:80, and the mixture was made into a 80mmx80mmx0.4mm resin sheet by melt casting (thermal curing conditions: temperature 200°C, pressure 70-80mmHg, time 30min), and the dielectric constant and dielectric loss tangent of the sample at a frequency of 10GHz were measured using an Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0110] Example 8

[0111] Example 9

[0112] Example 9

[0113] Example 9

[0114] Example 10

[0115] Example 10

[0116] Example 10

[0117] Example 10

[0118] Example 10

[0119] According to the same method and steps of patent CN1501899A example 1, using 3-vinyl benzyl chloride and 4-vinyl benzyl chloride mixture with mass ratio of 1:1 as raw material, a mixture of 9,9-bis(vinyl benzyl)-9H-fluorene containing meta and para isomers was synthesized, and the melting point was 142-145℃ after toluene recrystallization.

[0120] The prepared mixture of 9,9-bis(vinyl benzyl)-9H-fluorene containing meta and para isomers was made into 80mm×80mm×0.4mm resin sheet by melt casting method (thermal curing conditions: temperature 200℃, pressure 70-80mmHg, time 30min), and the dielectric constant and dielectric loss tangent of the sample at a frequency of 10GHz were determined by using the American Agilent N5230A type vector network analyzer, and the results are shown in Table 10.

[0121] Table 10 Dielectric constant D of resin sheet prepared in examples 5-10 and comparative examples 1-2 k (10GHz) and dielectric loss tangent D f (10GHz)

[0122] As can be seen from Table 10, the dielectric loss tangent of 9,9-bis(2-vinyl benzyl)-9H-fluorene is smaller than that of 9,9-bis(4-vinyl benzyl)-9H-fluorene, and the dielectric constant and dielectric loss tangent of both are much smaller than those of 1,2-bis(4-vinyl phenyl)ethane resin sample (comparative example 1) and bis(vinyl benzyl)-9H-fluorene containing meta (comparative example 2). For resin samples of different proportions of 9,9-bis(2-vinyl benzyl)-9H-fluorene and 9,9-bis(4-vinyl benzyl)-9H-fluorene, the higher the content of 9,9-bis(2-vinyl benzyl)-9H-fluorene, the lower the dielectric loss tangent of the resin, and when the content of 9,9-bis(2-vinyl benzyl)-9H-fluorene is ≥20wt%, the dielectric loss tangent of the resin is ≤0.00044. The double vinyl benzyl fluorene hydrocarbon resin provided in the present application has low dielectric constant and small dielectric loss tangent, and can be used as the main resin of high frequency substrate or crosslinking agent of alkenyl resin component.

[0123] The above only describes the preferred embodiments of the present application, and it should be pointed out that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which should also be considered as the protection scope of the present application.

Claims

1. A bisvinylbenzylfluorene, comprising 9,9-bis(2-vinylbenzyl)-9H-fluorene having the structure shown in Formula I or 9,9-bis(4-vinylbenzyl)-9H-fluorene having the structure shown in Formula II: The 9,9-bis(2-vinylbenzyl)-9H-fluorene has monoclinic crystal system. The 9,9-bis(4-vinylbenzyl)-9H-fluorene has triclinic crystal system.

2. The bisvinylbenzylfluorene of claim 1, wherein, The X-ray powder diffraction analysis characteristic peak 2θ of the 9,9-bis(2-vinylbenzyl)-9H-fluorene includes 11.9°, 12.3°, 14.2°, 15.4°, 18.5°, 19.2°, 20.0°, 20.7°, 22.2°, 23.7° and 24.7°.

3. The bisvinylbenzylfluorene according to claim 1 or 2, characterized in that, The space group of the 9,9-bis(2-vinylbenzyl)-9H-fluorene is P21 / c; the cell parameters are α = 90°, β = 96.243(2)°, γ = 90°.

4. The bisvinylbenzylfluorene of claim 1 or 2, wherein The melting point of the 9,9-bis(2-vinylbenzyl)-9H-fluorene is 124-126℃.

5. The bisvinylbenzylfluorene of claim 1, wherein, The X-ray powder diffraction analysis characteristic peak 2θ of the 9,9-bis(4-vinylbenzyl)-9H-fluorene includes 11.1°, 12.0°, 18.6°, 19.1°, 20.0°, 22.1°, 23.6°, 24.0° and 24.6°.

6. The bisvinylbenzylfluorene of claim 1 or 5, wherein The space group of the 9,9-bis(4-vinylbenzyl)-9H-fluorene is P2i The cell parameters are α = 94.299(2)°, β = 92.157(2)°, γ = 91.265(3)°.

7. The bisvinylbenzylfluorene of claim 1 or 5, wherein The melting point of the 9,9-bis(4-vinylbenzyl)-9H-fluorene is 118-120℃.

8. A method for preparing the divinylbenzyl fluorene according to any one of claims 1-7, comprising the following steps: The fluorene, vinylbenzyl chloride, basic reagent, polymerization inhibitor, phase transfer catalyst and organic solvent are mixed to carry out phase transfer reaction to obtain the divinylbenzyl fluorene; the vinylbenzyl chloride is 2-vinylbenzyl chloride or 4-vinylbenzyl chloride.

9. The preparation method according to claim 8, characterized in that, The phase transfer catalyst includes one or more of quaternary ammonium salt, quaternary phosphonium salt and polyethylene glycol; the mass of the phase transfer catalyst is 10-35% of the mass of the fluorene; The organic solvent includes one or more of aromatic hydrocarbon, aliphatic hydrocarbon, petroleum ether and acetonitrile.

10. The method of claim 9, wherein, The number average molecular weight of the polyethylene glycol is 200-600.

11. The preparation method according to claim 8, characterized in that, The basic reagent includes alkali metal hydroxide and / or alkali metal alcoholate; The molar ratio of the fluorene to the basic reagent is 1:1.8-5.

12. The method of any one of claims 8 to 11, wherein the method further comprises, The phase transfer reaction is carried out under stirring at a temperature of 25-45℃ for 12-18h.

13. The preparation method according to claim 8, characterized in that, The polymerization inhibitor includes one or more of nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, o-benzoquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butyl-o-benzoquinone, 2,2,6,6-tetramethylpiperidine N-oxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine N-oxide; The mass of the polymerization inhibitor is 0.01-0.5% of the mass of the vinylbenzyl chloride.

14. The method of claim 8, wherein, The molar ratio of the fluorene to the vinylbenzyl chloride is 1:2-2.

5.

15. Use of the divinylbenzyl fluorene in high-frequency substrates; the divinylbenzyl fluorene is the 9,9-bis(2-vinylbenzyl)-9H-fluorene having the structure shown in formula I or the 9,9-bis(4-vinylbenzyl)-9H-fluorene having the structure shown in formula II or a mixture of both in any ratio according to any one of claims 1-7.

16. The use according to claim 15, characterized in that, The use is the use as a crosslinking agent of a high-frequency substrate.

17. Use according to claim 16, characterized in that, The crosslinking agent is a crosslinking agent of an alkenyl resin component.

18. The use according to claim 17, characterized in that, The alkenyl resin component includes a terminal vinyl-modified polyphenyl ether.

19. A divinylbenzylfluorene hydrocarbon resin, prepared from a starting material comprising a divinylbenzylfluorene, said divinylbenzylfluorene being 9,9-bis(2-vinylbenzyl)-9H-fluorene having the structure of Formula I and / or 9,9-bis(4-vinylbenzyl)-9H-fluorene having the structure of Formula II: ###0002### ###0003### Formula I Formula II 20. The divinylbenzylfluorene hydrocarbon resin of claim 19, wherein, When the divinylbenzylfluorene is a mixture of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene, the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene in the mixture is ≥ 5 wt%.

21. The divinylbenzylfluorene hydrocarbon resin of claim 20, wherein, The content of 9,9-bis(2-vinylbenzyl)-9H-fluorene in the mixture is ≥ 10 wt%.

22. The divinylbenzylfluorene hydrocarbon resin according to claim 20 or 21, characterized in that, The content of 9,9-bis(2-vinylbenzyl)-9H-fluorene in the mixture is > 20 wt%.

23. A method for preparing the divinylbenzylfluorene hydrocarbon resin according to any one of claims 19 to 22, comprising the steps of: thermally curing the divinylbenzylfluorene to obtain the divinylbenzylfluorene hydrocarbon resin.

24. The method of claim 23, wherein, The thermal curing comprises melt sample casting.

25. The method of manufacturing according to claim 23 or 24, wherein, The thermal curing is performed at a temperature of 200 °C, a pressure of 70 to 80 mmHg, and for a time of 30 min.

26. Use of the divinylbenzylfluorene hydrocarbon resin according to any one of claims 19 to 22 or the divinylbenzylfluorene hydrocarbon resin prepared according to any one of claims 23 to 25 in a high frequency substrate.

27. The use according to claim 26, characterized in that, The use is as a main resin of a high frequency substrate.

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