A divinylbenzylfluorene and its preparation method and application, divinylbenzylfluorene hydrocarbon resin and its preparation method and application

Abstract

The present invention provides a divinylbenzylfluorene and a preparation method and application thereof, a divinylbenzylfluorene hydrocarbon resin and a preparation method and application thereof, and relates to the technical field of high-frequency substrate materials. The divinylbenzylfluorene hydrocarbon resin prepared by using one or a mixture of any proportion of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided by the present invention as raw materials 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; moreover, the solubility of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided by the present invention in toluene and 2-butanone is high, and has good application prospects as a cross-linking agent of the main resin or olefin resin component of a high-frequency substrate.

Description

Technical Field

[0001] The invention relates to the technical field of high-frequency substrate materials, and in particular to divinylbenzylfluorene and a preparation method and application thereof, and divinylbenzylfluorene hydrocarbon resin and a preparation method and application thereof. Background Art

[0002] Low dielectric constant (D k ) and low dielectric loss tangent (D f ) is a key material in the field of microelectronics such as high-frequency substrates and antennas. Modified polyphenylene ether (MPPO) terminated with vinylbenzyl or acryl has a low dielectric constant and dielectric loss tangent and is widely used as a laminate material for printed circuit boards (PCBs). However, with the rapid development of 5G / 6G communications, AR / VR and artificial intelligence, electronic products tend to require higher transmission speeds, frequencies 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 rates and signal integrity, printed circuit boards, the core components of electronic products, require resin materials with lower dielectric constants and lower dielectric loss tangents. Therefore, further reducing the dielectric constant and dielectric loss of resin materials is a key technical issue that needs to be solved urgently.

[0003] 9,9-Disubstituted fluorenyl hydrocarbon derivatives are widely used as materials for microelectronic devices due to their unique Cardo structure, 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.

[0004] JP2003283076A discloses a mixture prepared by reacting vinylbenzyl chloride and allyl chloride with fluorene, wherein the dielectric constant (5 GHz) of the thermosetting resin is 4.0, the dielectric loss tangent (5 GHz) is 0.0035, and the vinylbenzyl chloride 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°C prepared by reacting vinylbenzyl chloride with fluorene, wherein the dielectric constant (1 MHz) of the thermosetting resin is 2.65, the dielectric loss tangent (1 MHz) is 0.0013, and the vinylbenzyl chloride is a mixture of meta- and para-isomers in a mass ratio of 1:1. WO2022207741A1 discloses a thermosetting laminated material with a combination of vinylbenzyl indene and a 9,9-bisvinylbenzyl-9H-fluorene mixture containing meta isomers and bismaleimide, and the dielectric constant (10GHz) is 2.55 and the dielectric loss tangent (10GHz) is 0.00089. However, none of the above-mentioned 9,9-disubstituted fluorenyl hydrocarbon derivatives obtains a single isomer, and they are all mixtures containing meta isomers (9,9-bis(3-vinylbenzyl)-9H-fluorene). Due to the large molecular polarity and high melting point of the meta isomer of the 9,9-disubstituted fluorenyl hydrocarbon derivative, it has poor solubility in organic solvents and poor compatibility with olefinic resins, resulting in the dielectric loss tangent of the thermosetting resin being not low enough. Summary of the invention

[0005] In view of this, the object of the present invention is to provide a divinylbenzylfluorene and a preparation method and application thereof, a divinylbenzylfluorene hydrocarbon resin free of meta isomers and a preparation method and application thereof. The divinylbenzylfluorene provided by the present invention has high purity and does not contain meta isomers. The divinylbenzylfluorene hydrocarbon resin prepared using divinylbenzylfluorene as a raw material has a small dielectric loss tangent and a low dielectric constant.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a divinylbenzylfluorene, which is 9,9-bis(2-vinylbenzyl)-9H-fluorene (9,9-bis(2-vinylbenzyl)-9H-fluorene, abbreviated as o,o-BVBF) having a 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) having a structure shown in formula II:

[0008]

[0009] The 9,9-bis(2-vinylbenzyl)-9H-fluorene has a monoclinic crystal system;

[0010] The 9,9-bis(4-vinylbenzyl)-9H-fluorene has a triclinic crystal system.

[0011] The present invention also provides a method for preparing the divinylbenzylfluorene described in the above technical solution, comprising the following steps:

[0012] Fluorene, vinylbenzyl chloride, alkaline reagent, polymerization inhibitor, phase transfer catalyst and solvent are mixed to carry out phase transfer reaction to obtain the divinylbenzylfluorene; the vinylbenzyl chloride is 2-vinylbenzyl chloride or 4-vinylbenzyl chloride.

[0013] 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 to 35% of the mass of fluorene;

[0014] The organic solvent includes one or more of aromatic hydrocarbons, aliphatic hydrocarbons, petroleum ether and acetonitrile.

[0015] Preferably, the temperature of the phase transfer reaction is 25 to 45° C., the time is 12 to 18 hours, and the phase transfer reaction is carried out under stirring conditions.

[0016] Preferably, the polymerization inhibitor includes one or more of nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitroxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide;

[0017] The mass of the polymerization inhibitor is 0.01-0.5% of the mass of vinylbenzyl chloride.

[0018] Preferably, the molar ratio of fluorene to vinylbenzyl chloride is 1:2 to 2.5.

[0019] The present invention also provides a divinylbenzylfluorene hydrocarbon resin, the preparation raw materials include divinylbenzylfluorene, the divinylbenzylfluorene is 9,9-bis(2-vinylbenzyl)-9H-fluorene having a structure shown in formula I and / or 9,9-bis(4-vinylbenzyl)-9H-fluorene having a structure shown in formula II:

[0020]

[0021] Preferably, 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 %.

[0022] The present invention also provides a method for preparing the divinylbenzylfluorene hydrocarbon resin described in the above technical solution, comprising the following steps: thermally curing divinylbenzylfluorene to obtain the divinylbenzylfluorene hydrocarbon resin.

[0023] The present invention also provides the use of the divinylbenzylfluorene hydrocarbon resin described in the above technical solution or the divinylbenzylfluorene hydrocarbon resin prepared by the preparation method described in the above technical solution in a high-frequency substrate.

[0024] 9,9-Bisvinylbenzyl-9H-fluorene has a variety of isomers. The geometric properties of divinylbenzylfluorene isomers with different structures and their crystal forms will affect physical properties such as dielectric constant, dielectric loss tangent and solubility in organic solvents. The divinylbenzylfluorene provided by the present invention has a purity higher than 99%, high purity, and does not contain meta-isomers (9,9-bis(3-vinylbenzyl)-9H-fluorene shown in formula III, 9-(3-vinylbenzyl)-9-(4-vinylbenzyl)-9H-fluorene shown in formula IV).

[0025]

[0026] The 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided by the present invention can be dissolved in toluene and / or 2-butanone at room temperature (25°C) to form a transparent solution, and are suitable for use as a cross-linking agent for the vinyl resin component of a high-frequency substrate. The divinylbenzylfluorene hydrocarbon resin prepared using 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene as raw materials provided by the present invention has a low dielectric constant and a low dielectric loss tangent, and has a good application prospect as a cross-linking agent for the vinyl resin component of a high-frequency substrate (for example, terminal vinyl-modified polyphenylene ether cross-linking). As shown in the test results of the embodiment, the dielectric constant D of the divinylbenzylfluorene hydrocarbon resin using 9,9-bis(2-vinylbenzyl)-9H-fluorene as a raw material is 2.38kcal, 1.32kcal, and 1.66kcal, respectively. k (10GHz) is 2.8, dielectric loss tangent D f (10GHz) is 0.00032; the dielectric constant D of the bisvinylbenzylfluorene hydrocarbon resin made from 9,9-bis(4-vinylbenzyl)-9H-fluorene is k (10GHz) is 2.8, dielectric loss tangent D f(10GHz) is 0.00047, and the dielectric constant of bisvinylbenzylfluorene hydrocarbon resin is low and the dielectric loss angle is small.

[0027] The bisvinylbenzylfluorene hydrocarbon resin prepared from a mixture of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene in any proportion provided by the present invention also has a low dielectric constant and a 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 bisvinylbenzylfluorene hydrocarbon resin. When the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene is ≥20wt%, the dielectric loss tangent of the bisvinylbenzylfluorene hydrocarbon resin is ≤0.00044.

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

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

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

[0031] Figure 2 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 1 HNMR spectra;

[0032] Figure 3 DQF-COSY of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 1 H- 12D plot of H-correlation NMR spectrum;

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

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

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

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

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

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

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

[0040] Fig.11 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 1 HNMR spectra;

[0041] Fig.12 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 13 CNMR images;

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

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

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

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

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

[0047] The present invention 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]

[0049] In the present invention, the 9,9-bis(2-vinylbenzyl)-9H-fluorene (crystal) has a monoclinic system; the characteristic peaks 2θ of the X-ray powder diffraction analysis of the 9,9-bis(2-vinylbenzyl)-9H-fluorene preferably include: 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%.

[0050] In the present invention, the 9,9-bis(4-vinylbenzyl)-9H-fluorene (crystal) has a triclinic crystal system; the characteristic peaks 2θ of the X-ray powder diffraction analysis of the 9,9-bis(4-vinylbenzyl)-9H-fluorene preferably include: 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%.

[0051] The bisvinylbenzylfluorene 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 of any proportion of the two as raw materials provided by the present invention 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 bisvinylbenzylfluorene hydrocarbon resin; moreover, the 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene provided by the present invention have high solubility in toluene and 2-butanone. The mixture of one of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene or any proportion of the two as a crosslinking agent of an olefin resin component also has good application prospects. Bisvinylbenzylfluorene hydrocarbon resin prepared from one of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene or a mixture of the two has a good application prospect as the main resin of high-frequency substrate.

[0052] The invention provides a method for preparing divinylbenzylfluorene described in the above technical scheme, comprising the following steps: mixing fluorene, vinylbenzyl chloride, an alkaline reagent, a polymerization inhibitor, a phase transfer catalyst and an organic solvent, and performing a phase transfer reaction to obtain the divinylbenzylfluorene; the vinylbenzyl chloride is 2-vinylbenzyl chloride or 4-vinylbenzyl chloride.

[0053] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0054] In the present invention, the molar ratio of fluorene to 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 present invention, both 2-vinylbenzyl chloride (CAS: 22570-84-9) and 4-vinylbenzyl chloride (CAS: 1592-20-7) are produced by Shandong Xingshun New Materials Co., Ltd.; the purity of 2-vinylbenzyl chloride is preferably 99.0%, and the purity of 4-vinylbenzyl chloride is preferably 99.5%.

[0055] In the present invention, the alkaline agent preferably includes an alkali metal hydroxide and / or an alkali metal alkoxide; 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 alkoxide 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 present invention, the molar ratio of fluorene to the alkaline agent is preferably 1:1.8-5, more preferably 1:2-4, and most preferably 1:2-3.

[0056] In the present invention, the polymerization inhibitor preferably includes one or more of nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitroxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide (inhibitor 701). In the present invention, the mass of the polymerization inhibitor is preferably 0.01-0.5% of the mass of vinylbenzyl chloride, more preferably 0.1-0.4%, and most preferably 0.2-0.3%.

[0057] In the present invention, the phase transfer catalyst preferably includes one or more of quaternary ammonium salts, quaternary phosphonium salts and polyethylene glycol (PEG), more preferably polyethylene glycol; the number average molecular weight of the polyethylene glycol is preferably 200-600, more preferably 400-600; the polyethylene glycol specifically preferably includes one or more of PEG-200, PEG-400 and PEG-600. In the present invention, the mass of the transfer catalyst is preferably 10-35% of the mass of fluorene, more preferably 20-30%.

[0058] In the present invention, the organic solvent preferably includes one or more of aromatic hydrocarbons, aliphatic hydrocarbons, petroleum ether and acetonitrile, and more preferably aromatic hydrocarbons or acetonitrile; the aromatic hydrocarbons preferably include one or more of toluene, xylene and ethylbenzene, and more preferably toluene; the aliphatic hydrocarbons preferably include one or more of cyclohexane, n-hexane and n-heptane. In the present invention, the ratio of the mass of the fluorene to the volume of the organic solvent is preferably 1g:3-8mL, and more preferably 1g:5mL.

[0059] In the present invention, 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 12-18h, more preferably 13-16h, and further preferably 14-15h; the phase transfer reaction is preferably carried out under stirring conditions, and the stirring speed is preferably 200-500r / min, and more preferably 300-400r / min. In a specific embodiment of the present invention, the phase transfer reaction is stopped when the content of fluorene in the reaction system is less than 1wt%.

[0060] After completing the phase transfer reaction, the present invention preferably further comprises post-treatment, and the post-treatment preferably comprises: first concentrating the reaction system obtained by the phase transfer reaction, adding water and toluene for layering, washing the obtained organic phase with a saturated ammonium chloride solution, washing with water until neutral, second concentrating, recrystallizing and solid-liquid separation, and drying the obtained solid component to obtain the divinylbenzylfluorene hydrocarbon resin.

[0061] The present invention has no particular limitation on the first concentration and the second concentration. A concentration method well known to those skilled in the art may be used to remove the solvent, such as evaporation or reduced pressure distillation.

[0062] In the present invention, the solvent used for the recrystallization preferably includes one or more of aromatic hydrocarbon solvents, ketone solvents, ether solvents, alcohol solvents and acetonitrile; the aromatic hydrocarbon solvent preferably includes one or more of toluene, xylene, ethylbenzene and isopropylbenzene; the ketone solvent preferably includes one or more of acetone, 2-butanone and methyl isobutyl ketone; the ether solvent preferably includes one or more of methyl tert-butyl ether, tetrahydrofuran, methyltetrahydrofuran and anisole; the alcohol solvent preferably includes one or more of methanol, ethanol and isopropanol; the solvent used for the recrystallization is more preferably a toluene-methanol mixed solvent or a toluene-acetonitrile mixed solvent; the volume ratio of toluene and methanol in the toluene-methanol mixed solvent is preferably 1:0.1-0.6, more preferably 1:0.2-0.4; the volume ratio of toluene and acetonitrile in the toluene-acetonitrile mixed solvent is preferably 1:0.1-0.6, more preferably 1:0.2-0.4. In the present invention, the recrystallization preferably includes: heating to complete dissolution, cooling to -10 to 20°C for constant temperature crystallization; the cooling rate of the cooling is preferably 0.2 to 1°C / min, more preferably 0.4 to 0.5°C / min; the temperature of the constant temperature crystallization is more preferably 5 to 10°C.

[0063] The present invention has no special limitation on the solid-liquid separation, and any solid-liquid separation method well known to those skilled in the art may be used, such as filtration, suction filtration or centrifugal separation.

[0064] In the present invention, the drying temperature is preferably 70 to 110° C., more preferably 80 to 90° C.; the present invention has no particular limitation on the drying time, and the drying time may be until constant weight.

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

[0066]

[0067] In the present invention, when the divinylbenzylfluorene is a mixture of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene, the present invention has no special limitation 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 is acceptable. Specifically, the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene in the mixture is preferably ≥5wt%, more preferably ≥10wt%, most preferably ≥10wt%, and specifically preferably 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt% or 95wt%. In the present invention, 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. When the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene is greater than 20wt%, the D k (10GHz) is 2.8, D f (10GHz)<0.00044.

[0068] The present invention also provides a method for preparing the divinylbenzylfluorene hydrocarbon resin described in the above technical solution, comprising the following steps: thermally curing divinylbenzylfluorene to obtain the divinylbenzylfluorene hydrocarbon resin.

[0069] In the present invention, the thermal curing preferably includes a molten sample casting method. In the present invention, the thermal curing temperature is preferably 200° C., the pressure is preferably 70-80 mmHg, and the time is preferably 30 min.

[0070] The present invention also provides the use of the divinylbenzylfluorene described in the above technical solution, the divinylbenzylfluorene obtained by the preparation method described in the above technical solution, the divinylbenzylfluorene hydrocarbon resin described in the above technical solution, or the divinylbenzylfluorene hydrocarbon resin obtained by the preparation method described in the above technical solution in high-frequency substrates. In the present invention, the application is preferably used as the main resin or cross-linking agent of the high-frequency substrate; the cross-linking agent is preferably a cross-linking agent of an olefinic resin component, and the olefinic resin component preferably includes terminal vinyl-modified polyphenylene ether. In the present invention, the divinylbenzylfluorene is preferably used as a cross-linking agent for high-frequency substrates; the divinylbenzylfluorene hydrocarbon resin is preferably used as the main resin of high-frequency substrates.

[0071] The bisvinylbenzylfluorene 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 proportion as raw materials provided by the present invention 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 bisvinylbenzylfluorene hydrocarbon resin; moreover, the 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene and a mixture thereof in any proportion provided by the present invention can be dissolved in toluene and 2-butanone at a mass ratio of 1:1 between the compound and the solvent to form a transparent solution, and has high solubility in toluene and 2-butanone, and has good application prospect as a main resin or a crosslinking agent of an olefin resin component of a high-frequency substrate.

[0072] To further illustrate the present invention, a divinylbenzylfluorene and a preparation method and application thereof, a divinylbenzylfluorene hydrocarbon resin and a preparation method and application thereof provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0073] In the following examples, 2-vinylbenzyl chloride (HPLC purity is 99.0%, produced by Shandong Xingshun New Materials Co., Ltd.), 4-vinylbenzyl chloride (HPLC purity is 99.5%, produced by Shandong Xingshun New Materials Co., Ltd.).

[0074] Analytical instruments and analytical test methods used:

[0075] 1. Purity determination method (HPLC): American Agillent 1260 high pressure liquid chromatograph; column type: Kromasil 100-5 C18 250 cm × 4.6 mm; mobile phase: acetonitrile / methanol volume ratio = 9:1; flow rate: 0.8 mL / min; detection wavelength: 254 nm; injection volume: 2 μL; pump mode: binary high pressure gradient.

[0076] 2. Thermal analysis method: DSC was measured using a Pyris1 thermal analyzer (Perkin Elemer) with a heating range of 50-200°C and a heating rate of 10°C / min.

[0077] 3. Nuclear magnetic resonance spectrum determination: Bruker AV 400 nuclear magnetic resonance instrument, DMSO-d6 as solvent, TMS as internal standard.

[0078] 4. Infrared spectrometry: NEXUS870 Fourier transform infrared spectrometer (FT-IR) (NICOLET), potassium bromide tablets.

[0079] 5. Single crystal structure determination: Bruker D8 Venture single crystal diffractometer, JY / T0588-2020 General rules for molecular structure analysis methods.

[0080] 6. Dielectric constant D k (10GHz) and dielectric loss tangent D f (10GHz) measurement: The molten sample casting method (thermal curing conditions: temperature 200°C, pressure 70-80 mmHg, time 30 min) was used to make 80mm×80mm×0.4mm resin sheets, and the samples were measured at a frequency of 10GHz using an Agilent N5230A vector network analyzer.

[0081] 7. X-ray powder diffraction spectrum determination: Bruker D2 Phaser polycrystal diffractometer, JY / T0587-2020 General principles for analytical methods.

[0082] Example 1

[0083] Add 500 mL of acetonitrile, 1.4 mol of potassium hydroxide powder, 30 g of PEG-400, and 0.5 g of inhibitor 701 into a reaction flask, and add 0.6 mol of fluorene and 1.4 mol of 2-vinylbenzyl chloride (HPLC, 99%) under stirring conditions. React at 30-35°C and 350 r / min stirring conditions until the fluorene content is less than 1 wt% according to HPLC analysis. The reaction was stopped, acetonitrile was evaporated, and 500 mL of water and 500 mL of toluene were added, the layers were separated, the organic phase was washed with saturated ammonium chloride solution, and washed with water 3 times (each time with 500 mL of water) until neutral, the toluene was evaporated under reduced pressure, and a mixed solvent of toluene and methanol in a volume ratio of 1:0.3 was added, heated until completely dissolved, cooled to 5°C at a rate of 0.5°C / min, and crystallized at a constant temperature, filtered, and the obtained solid component was dried at 90°C to constant weight to obtain 191.5 g of 9,9-bis(2-vinylbenzyl)-9H-fluorene, o,o-BVBF, white crystals, HPLC purity ( Figure 1 and Table 1) is 99.4%, melting point (thermal analysis DSC melting absorption peak, Figure 6 ) is 124.0~125.5℃; the yield is 80.1%.

[0084] Table 1 HPLC peak information of o,o-BVBF

[0085] peak Retention time / min type Peak width / min Peak area / mAU·s Peak height / mAU Peak area / % 1 4.325 VB 0.1261 2.05417 0.258843 0.0310 2 5.185 VB 0.1087 3.17340 0.449067 0.0479 3 6.018 BV 0.1136 1.13122 0.153654 0.0171 4 6.507 VV 0.1195 6589.77441 850.62708 99.3721 5 7.329 VB 0.1429 26.97264 2.87846 0.4067 6 8.833 VB 0.1790 6.40461 0.506698 0.0966 7 10.762 BB 0.2181 1.90339 0.115719 0.0287

[0086] Figure 2 For o,o-BVBF 1 HNMR diagram, Figure 3 DQF-COSY for o,o-BVBF 1 H- 1H-correlation NMR spectrum 2D diagram, Figure 4 For o,o-BVBF 13 C NMR spectrum, Figure 5 This is the FT-IR graph of o,o-BVBF. 1 H NMR (400 MHz, DMSO-d6) δ: 3.54 (s, 4H, 2×CH2), 5.10 (d, 2H, 2×olefin terminal hydrogen), 5.42 (d, 2H, 2×olefin terminal hydrogen), 6,54 (d, 2H, 2×benzene ring hydrogen), 6.79-6.87 (m, 4H, 2×benzene ring hydrogen, 2×CH=CH2), 6.97-7.01 (m, 2H, 2×benzene ring hydrogen), 7.15-7.19 (m, 2H, 2×fluorene ring hydrogen), 7.22-7.24 (m, 2H, 2×benzene ring hydrogen), 7.25-7.29 (m, 2H, 2×fluorene ring hydrogen), 7.40 (d, 2H, 2×fluorene ring hydrogen), 7.60 (d, 2H, 2×fluorene 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).

[0087] Figure 7 This is the single crystal structure diagram of o,o-BVBF. Figure 8 is the unit cell stacking diagram of o,o-BVBF, Fig. 9 is the X-ray powder diffraction spectrum of o,o-BVBF, and the crystallographic parameters of o,o-BVBF are shown in Tables 2 to 5. It can be seen that the single crystal structure of o,o-BVBF is determined to be white monoclinic crystals, and the characteristic peaks 2θ (relative intensity %) of X-ray powder diffraction analysis are: 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).

[0088] Table 2 Crystallographic table of o,o-BVBF and p,p-BVBF

[0089]

[0090] Table 3 Atomic coordinates of o,o-BVBF (×10 4 ) and equivalent isotropic displacement parameter

[0091]

[0092]

[0093] Table 4 Bond lengths of o,o-BVBF and bond angle [°]

[0094]

[0095]

[0096] Table 5 Anisotropic displacement parameters of o,o-BVBF

[0097]

[0098]

[0099] Example 2

[0100] Add 500 mL acetonitrile, 1.4 mol potassium tert-butoxide, 30 g PEG-400, 0.5 g inhibitor 701 into the reaction bottle, add 0.6 mol fluorene and 1.4 mol 2-vinylbenzyl chloride (HPLC, 99%) under stirring conditions, and react at 30-35°C and 350 r / min stirring conditions until the fluorene content is less than 1 wt% according to HPLC analysis. The reaction was stopped, acetonitrile was evaporated, 500 mL of water and 500 mL of toluene were added, the layers were separated, the organic phase was washed with saturated ammonium chloride solution, washed with water 3 times (each time with 500 mL of water) until neutral, toluene was evaporated under reduced pressure, a mixed solvent of toluene and methanol in a volume ratio of 1:0.3 was added, heated until completely dissolved, cooled to 5°C at a rate of 0.5°C / min, constant temperature crystallization was performed, filtered, and the obtained solid component was dried at 90°C to constant weight to obtain 199.5 g of 9,9-bis(2-vinylbenzyl)-9H-fluorene as white crystals with an HPLC purity of 99.5% and a yield of 83.5%.

[0101] Example 3

[0102] 350 mL of acetonitrile, 1.4 mol of potassium hydroxide powder, 30 g of PEG-400, and 0.5 g of inhibitor 701 were added to a reaction bottle, and 0.6 mol of fluorene and 1.4 mol of 4-vinylbenzyl chloride (HPLC 99.5%) were added under stirring. The mixture was stirred 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, acetonitrile was evaporated, 500 mL of water and 500 mL of toluene were added, and the organic phase was washed with saturated ammonium chloride solution and washed with water 3 times (each time with 500 mL of water) until neutral. Toluene was evaporated under reduced pressure, and a mixed solvent of toluene and methanol in a volume ratio of 1:0.3 was added, heated until completely dissolved, cooled to 5°C at a rate of 0.5°C / min, and crystallized at a constant temperature. The solid component was filtered and dried at 90°C to constant weight to obtain 197.6 g of 9,9-bis(4-vinylbenzyl)-9H-fluorene, p,p-BVBF as white crystals with HPLC purity of ( Fig.10 and Table 6) is 99.7%, the melting point is 118.4-119.8°C (thermal analysis DSC melting absorption peak, Fig.13 ), with a yield of 82.6%.

[0103] Table 6 HPLC peak information of p,p-BVBF

[0104] peak Retention time (min) type Peak width (min) Peak area (mAU·s) Peak height (mAU) Peak area (%) 1 3.877 BV 0.0959 1.13256 0.182081 0.0140 2 4.908 VB 0.1015 2.72516 0.406471 0.0338 3 5.507 BB 0.1120 3.14688 0.428014 0.0390 4 6.024 BV 0.1122 8043.53857 1110.62878 99.7056 5 6.507 VB 0.1244 3.88065 0.461084 0.0481 6 7.440 BV 0.2139 2.31902 0.147576 0.0287 7 8.036 VB 0.1490 9.18154 0.939460 0.1138 8 16.566 BB 0.2406 1.36443 0.0691055 0.0169

[0105] Fig.11 For p,p-BVBF 1 H NMR spectrum, Fig.12 For p,p-BVBF 13 C NMR spectrum, Fig.14 This is the FT-IR graph of p,p-BVBF. 1 H NMR (400 MHz, DMSO-d6) δ: 3.48 (s, 4H, 2×CH2), 5.08 (d, 2H, 2×olefin terminal hydrogen), 5.61 (d, 2H, 2×olefin terminal hydrogen), 6.45-6.52 (m, 2H, 2×CH=CH2), 6.57 (d, 4H, 4×benzene ring hydrogen), 6.96 (d, 4H, 4×benzene ring hydrogen), 7.20-7.24 (m, 2H, 2×fluorene ring hydrogen), 7.34-7.37 (m, 2H, 2×fluorene ring hydrogen), 7.47 (d, 2H, 2×fluorene ring hydrogen), 7.77 (d, 2H, 2×fluorene ring hydrogen). 13C 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 (benzene ring C, fluorene ring C, vinyl C).

[0106] Fig.15 is the single crystal structure diagram of p,p-BVBF, Fig.16 is the unit cell stacking diagram of p,p-BVBF, Fig.17 The X-ray powder diffraction spectrum of p,p-BVBF is shown in Table 2 and Table 7 to Table 9. It can be seen that the single crystal of p,p-BVBF is white triclinic crystal, and the characteristic peaks 2θ (relative intensity %) of X-ray powder diffraction analysis 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).

[0107] Table 7 Atomic coordinates of p, p-BVBF (×10 4 ) and equivalent isotropic displacement parameter

[0108]

[0109]

[0110] Table 8 Bond lengths of p, p-BVBF and bond angle [°]

[0111]

[0112]

[0113] Table 9 Anisotropic displacement parameters of p,p-BVBF

[0114]

[0115]

[0116]

[0117] Example 4

[0118] 350 mL of acetonitrile, 1.4 mol of potassium tert-butoxide, 30 g of PEG-400, and 0.5 g of inhibitor 701 were added to a reaction bottle, 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 and 350 r / min with stirring until the content of fluorene according to HPLC analysis was less than 1wt%, the reaction was stopped, acetonitrile was evaporated, 500 mL of water and 500 mL of toluene were added, and the organic phase was layered. The obtained organic phase was washed with saturated ammonium chloride solution and washed with water for 3 times (each time with 500 mL of water) until neutral. The toluene was evaporated under reduced pressure, and a toluene-methanol mixed solvent with a volume ratio of 1:0.3 was used to heat and completely dissolve. The temperature was lowered to 5°C at a rate of 0.5°C / min to crystallize at a constant temperature, filtered, and the obtained solid component was dried at 90°C to constant weight to obtain 202.3 g of 9,9-bis(4-vinylbenzyl)-9H-fluorene as white crystals with an HPLC purity of 99.5% and a yield of 84.5%.

[0119] The hydrogen nuclear magnetic resonance spectrum of the synthesized divinylbenzylfluorene product of the present invention is ( 1 HNMR), carbon spectrum ( 13 The C NMR) infrared spectrum (FT-IR) was completely consistent with the structures of the single isomers of divinylbenzylfluorene, 9,9-bis(2-vinylbenzyl)-9H-fluorene (o,o-BVBF) and 9,9-bis(4-vinylbenzyl)-9H-fluorene (p,p-BVBF), respectively. The attribution of each peak in the H NMR spectrum of o,o-BVBF was determined by DQF-COSY 1 H- 1 The single crystal structure of the product obtained by recrystallization from a mixed solvent of toluene and methanol (volume ratio = 1:1) was determined by a two-dimensional H-correlated nuclear magnetic resonance spectrum. The single crystal structure of the product obtained by recrystallization from a mixed solvent of toluene and methanol (volume ratio = 1:1) was determined by a Bruker D8 Venture single crystal diffractometer, further confirming that the present invention successfully prepared single isomers 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene.

[0120] 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 a clear transparent solution. The mass ratio of divinylbenzylfluorene to toluene is 1:1, and the mass ratio of divinylbenzylfluorene to 2-butanone is 1:1. The crosslinking agent 1,2-bis(4-vinylphenyl)ethane (BVPE, CAS: 48174-52-3) commonly used in printed circuit board resins and the meta-position-containing divinylbenzylfluorene isomer in the control example 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 by the present invention in organic solvents is much greater than that of 1,2-bis(4-vinylphenyl)ethane and the meta-position divinylbenzylfluorene isomer.

[0121] Example 5

[0122] The 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 was made into a 80mm×80mm×0.4mm resin sheet by melt casting (thermal curing conditions: temperature of 200°C, pressure of 70-80mmHg, and time of 30min). 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.

[0123] Example 6

[0124] The 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 was made into a 80mm×80mm×0.4mm resin sheet by melt casting (thermal curing conditions: temperature of 200°C, pressure of 70-80mmHg, and time of 30min). 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.

[0125] Example 7

[0126] 20 wt% of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 and 80 wt% of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 were made into 80 mm×80 mm×0.4 mm resin sheets by melt casting (thermal curing conditions: temperature of 200°C, pressure of 70-80 mmHg, and time of 30 min). The dielectric constant and dielectric loss tangent of the samples at a frequency of 10 GHz were measured by an Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0127] Example 8

[0128] 40 wt% of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 and 60 wt% of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 were made into 80 mm×80 mm×0.4 mm resin sheets by melt casting (thermal curing conditions: temperature of 200°C, pressure of 70-80 mmHg, and time of 30 min). The dielectric constant and dielectric loss tangent of the samples at a frequency of 10 GHz were measured by an Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0129] Example 9

[0130] 60 wt% of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 and 40 wt% of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 were made into 80 mm×80 mm×0.4 mm resin sheets by melt casting (thermal curing conditions: temperature of 200°C, pressure of 70-80 mmHg, and time of 30 min). The dielectric constant and dielectric loss tangent of the samples at a frequency of 10 GHz were measured by an Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0131] Example 10

[0132] 80 wt% of 9,9-bis(2-vinylbenzyl)-9H-fluorene prepared in Example 1 and 20 wt% of 9,9-bis(4-vinylbenzyl)-9H-fluorene prepared in Example 3 were made into 80 mm×80 mm×0.4 mm resin sheets by melt casting (thermal curing conditions: temperature of 200°C, pressure of 70-80 mmHg, and time of 30 min). The dielectric constant and dielectric loss tangent of the samples at a frequency of 10 GHz were measured by an Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0133] Comparative Example 1

[0134] 1,2-bis(4-vinylphenyl)ethane (BVPE) was made into a 80mm×80mm×0.4mm resin sheet by melt casting (thermal curing conditions: temperature of 200°C, pressure of 70-80mmHg, and time of 30min). The dielectric constant and dielectric loss tangent of the sample at a frequency of 10GHz were measured by Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0135] Comparative Example 2

[0136] According to the same method and steps as Example 1 of patent CN1501899A, a mixture of 3-vinylbenzyl chloride and 4-vinylbenzyl chloride in a mass ratio of 1:1 was used as a raw material to synthesize a mixture of 9,9-bis(vinylbenzyl)-9H-fluorene containing meta- and para-isomers, with a melting point of 142-145°C after recrystallization from toluene.

[0137] The obtained mixture of 9,9-bis(vinylbenzyl)-9H-fluorene containing meta- and para-isomers was made into a 80mm×80mm×0.4mm resin sheet by melt casting method (thermal curing conditions: temperature is 200°C, pressure is 70-80mmHg, and time is 30min). The dielectric constant and dielectric loss tangent of the sample at a frequency of 10GHz were measured by Agilent N5230A vector network analyzer. The results are shown in Table 10.

[0138] Table 10 Dielectric constant D of resin sheets prepared in Examples 5 to 10 and Comparative Examples 1 to 2 k (10GHz) and dielectric loss tangent D f (10GHz)

[0139] Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 <![CDATA[D k (10GHz)]]> 2.8 2.8 2.8 2.8 2.8 2.8 3.2 2.8 <![CDATA[D f (10GHz)]]> 0.00032 0.00047 0.00044 0.00041 0.00038 0.00035 0.00080 0.00065

[0140] It can be seen from Table 10 that the dielectric loss tangent of 9,9-bis(2-vinylbenzyl)-9H-fluorene is smaller than that of 9,9-bis(4-vinylbenzyl)-9H-fluorene, and the dielectric constant and dielectric loss tangent of both are much smaller than those of the 1,2-bis(4-vinylphenyl)ethane resin sample (Comparative Example 1) and the meta-containing bis(vinylbenzyl)-9H-fluorene (Comparative Example 2). For the resin sample test of different proportions of mixtures of 9,9-bis(2-vinylbenzyl)-9H-fluorene and 9,9-bis(4-vinylbenzyl)-9H-fluorene, the higher the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene, the lower the dielectric loss tangent of the resin. When the content of 9,9-bis(2-vinylbenzyl)-9H-fluorene is ≥20wt%, the dielectric loss tangent of the resin is ≤0.00044. The bisvinylbenzylfluorene hydrocarbon resin provided by the present invention has a low dielectric constant and a small dielectric loss tangent, and can be used as a main resin of a high-frequency substrate or a cross-linking agent of an olefinic resin component.

[0141] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. 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: The 9,9-bis(2-vinylbenzyl)-9H-fluorene has a monoclinic crystal system; The 9,9-bis(4-vinylbenzyl)-9H-fluorene has a triclinic crystal system.

2. The method for preparing divinylbenzylfluorene according to claim 1, comprising the following steps: Fluorene, vinylbenzyl chloride, alkaline reagent, polymerization inhibitor, phase transfer catalyst and organic solvent are mixed and phase transfer reaction is carried out to obtain the divinylbenzylfluorene; the vinylbenzyl chloride is 2-vinylbenzyl chloride or 4-vinylbenzyl chloride.

3. The preparation method according to claim 2, characterized in that: The phase transfer catalyst comprises one or more of a quaternary ammonium salt, a quaternary phosphonium salt and polyethylene glycol; the mass of the phase transfer catalyst is 10 to 35% of the mass of fluorene; The organic solvent includes one or more of aromatic hydrocarbons, aliphatic hydrocarbons, petroleum ether and acetonitrile.

4. The preparation method according to claim 2 or 3, characterized in that: The temperature of the phase transfer reaction is 25-45° C., the time is 12-18 hours, and the phase transfer reaction is carried out under stirring conditions.

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

6. The preparation method according to claim 2, characterized in that: The molar ratio of fluorene to vinylbenzyl chloride is 1:2-2.

5.

7. A divinylbenzylfluorene hydrocarbon resin, wherein the raw materials for preparation include divinylbenzylfluorene, wherein the divinylbenzylfluorene is 9,9-bis(2-vinylbenzyl)-9H-fluorene having a structure shown in formula I and / or 9,9-bis(4-vinylbenzyl)-9H-fluorene having a structure shown in formula II:

8. The bisvinylbenzylfluorene hydrocarbon resin according to claim 7, characterized in that: When the bisvinylbenzylfluorene 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 %.

9. The method for preparing the divinylbenzylfluorene hydrocarbon resin according to claim 7 or 8, comprising the following steps: The divinylbenzylfluorene is thermally cured to obtain the divinylbenzylfluorene hydrocarbon resin.

10. Use of the divinylbenzylfluorene hydrocarbon resin according to claim 7 or 8 or the divinylbenzylfluorene hydrocarbon resin prepared by the preparation method according to claim 9 in high-frequency substrates.

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