Asymmetric divinylbenzyl fluorene, thermosetting hydrocarbon resin, thermosetting crosslinked resin, and method for preparing same and applications thereof

Abstract

The present invention belongs to the technical field of high-frequency, high-speed substrate materials and provides asymmetric divinylbenzyl fluorene (9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene, o, p-BVBF) and a thermosetting hydrocarbon resin thereof, and a method for manufacturing the same and an application thereof. At the same time, it provides a thermosetting hydrocarbon resin of o, p-BVBF and symmetric divinylbenzyl fluorene (9, 9'-bis(4-vinylbenzyl)-9H-fluorene, p, p-BVBF) and a thermosetting crosslinked resin of terminal alkenyl polyphenylene ether using o, p-BVBF and / or p, p-BVBF as a crosslinking agent, and a method for manufacturing the same and an application thereof.

Description

Technology Field

[0001] The present invention belongs to the field of high-frequency high-speed substrate material technology, and specifically relates to asymmetric divinylbenzyl fluorene, thermosetting hydrocarbon resin, thermosetting crosslinked modified polyphenylene ether resin, and methods for manufacturing the same and applications. Background Technology

[0002] With the rapid advancement of 5G / 6G communication, artificial intelligence, AR / VR, satellite navigation, and autonomous driving, electronic products require high frequencies, high speeds, and larger capacities to transmit sound, video, and data. At the same time, electronic products are evolving to become lighter, thinner, and smaller. To maintain higher transmission speeds and signal integrity, laminated resin materials for printed circuit boards (PCBs), which are core components of electronic products, must possess lower dielectric constant, lower dielectric loss tangent, higher glass transition temperatures, and stronger peel strength. Therefore, further improving the dielectric and thermomechanical properties of resin materials is a critical technical issue that currently needs to be addressed urgently.

[0003] Epoxy resin is a resin material primarily used in printed circuit boards due to its low cost; however, due to its relatively high dielectric constant and high dielectric loss tangent, it is difficult to achieve an appropriate low dielectric loss tangent for high-frequency signals and to meet the requirements for high-speed signal transmission. Fluoropolymers, represented by polytetrafluoroethylene, have characteristics of low dielectric constant and low dielectric loss tangent, but because they are thermoplastic resins, processing and molding for the manufacture of multilayer, lightweight, thin, and small printed circuit boards are difficult. Low molecular weight vinylbenzyl or acrylic-terminated polyphenylene ether (mPPO) exhibits low dielectric constant and dielectric loss tangent, and polyphenylene ether crosslinked resins crosslinked with mPPO and diene (e.g., 1,2-bis(4-vinylphenyl)ethane, BVPE) show high thermomechanical properties and have been used as resin materials for high-grade printed circuit board (PCB) laminates.

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

[0005] Japanese Patent JP2003283076A discloses a mixture prepared by reacting vinylbenzyl chloride (a mixture of meta and para isomers in a mass ratio of 1:1) and allyl chloride with fluorene; the dielectric constant (5 GHz) of the said thermosetting resin is 4.0 and the dielectric loss tangent (5 GHz) is 0.0035, which is clearly too high for both the dielectric constant and the dielectric loss tangent. At the same time, the presence of an allyl group on the 9-fluorene group lowers the glass transition temperature of the compound. Patent WO2022207741A1 discloses a thermosetting resin using a mixture of 9,9-divinylbenzyl-9H-fluorene containing vinylbenzyl indene and a meta isomer, with a dielectric loss tangent (10 GHz) of 0.00089. However, for resins used for high-frequency and high-speed substrates, the dielectric constant and dielectric loss tangent remain high. In addition, patent WO2022207741A1 uses bismaleimide as a crosslinking agent to increase the glass transition temperature; while bismaleimide contains polar groups that can increase the glass transition temperature, it results in an increase in the dielectric loss tangent. CN1501899A discloses a mixture of meta and para isomers of 9,9-bis(vinylbenzyl)-9H-fluorene with a melting point of 142°C, prepared by reacting fluorene with a mixture of vinylbenzyl chloride (mass ratio of meta and para isomers 1:1). The dielectric loss tangent (1 MHz) of the said thermosetting resin is 0.0013, which is clearly high and therefore unsuitable for use as a resin material for high-frequency and high-speed substrates.

[0006] To meet the high-frequency and high-speed transmission requirements of next-generation printed circuit boards, further lowering the dielectric constant and dielectric loss tangent of printed circuit board resin materials, and further raising the glass transition temperature, is a critical technical problem that must be urgently solved. The problem to be solved

[0007] In light of this, the present invention provides asymmetric divinylbenzyl fluorene, a thermosetting hydrocarbon resin using asymmetric divinylbenzyl fluorene as a raw material, a method for manufacturing the same, and applications, a thermosetting hydrocarbon resin using asymmetric divinylbenzyl fluorene and / or symmetric divinylbenzyl fluorene as a raw material, a method for manufacturing the same, and applications, and also provides a thermosetting crosslinked polyphenylene ether resin using asymmetric divinylbenzyl fluorene, symmetric divinylbenzyl fluorene, or a mixture of both as a crosslinking agent and crosslinked with terminal alkenyl polyphenylene ether, a method for manufacturing the same, and applications. The asymmetric divinylbenzyl fluorene (9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene, o, p-BVBF) provided in the present invention is a nonpolar all-hydrocarbon compound, and since two asymmetric substituents at the 9-position of fluorene form a rigid cardo structure, the thermosetting hydrocarbon resin and thermosetting cross-linked polyphenylene ether resin prepared using it have a small dielectric loss tangent, a low dielectric constant, a high glass transition temperature, and excellent application prospects as a resin material for high-frequency high-speed substrates. means of solving the problem

[0008] To solve the above technical problem, the present invention provides an asymmetric divinylbenzyl fluorene, which is 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene having a structure represented by Chemical Formula 1.

[0010] Equation 1

[0011] The above 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene has a thermal analysis melting endothermic peak of 169–175°C, has a monoclinic system, and its space group is P21 / c.

[0012] The present invention also provided a method for producing asymmetric divinylbenzyl fluorene according to the above technical plan, and

[0013] A step of obtaining a fluorene-containing mixture system by mixing fluorene, a basic reagent, a polymerization inhibitor, and a polar aprotic solvent, and

[0014] The method includes the step of obtaining the asymmetric divinylbenzyl fluorene by sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the mixture containing the fluorene, or by adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the mixture containing the fluorene to carry out a nucleophilic substitution reaction.

[0015] Preferably, the basic reagent comprises one or more of alkali metal hydroxide, alkali metal alkoxide, sodium hydride, and potassium hydride, and

[0016] The polymerization inhibitor 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-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide, and

[0017] The above polar aprotic solvent comprises dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, or hexamethylphosphoramide, and

[0018] The molar ratio of the above fluorene to the basic reagent is 1:1.8 to 5, and

[0019] The molar ratio of the above 2-vinylbenzyl chloride and 4-vinylbenzyl chloride is 2~6:4~8, and

[0020] The total moles of the above 2-vinylbenzyl chloride and 4-vinylbenzyl chloride and the molar ratio of fluorene is 1.8 to 2.2:1.

[0021] Preferably, the temperature of the nucleophilic substitution reaction is 20 to 50°C and the time is 2 to 8 hours.

[0022] The present invention also provided a method for producing asymmetric divinylbenzyl fluorene according to the above technical plan, and

[0023] A step of obtaining a fluorene-containing phase transition catalyst system by mixing fluorene, a basic reagent, a polymerization inhibitor, a phase transition catalyst, and a solvent, and

[0024] The method includes the step of sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the fluorene-containing phase transition catalyst system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the fluorene-containing phase transition catalyst system, and carrying out a nucleophilic substitution reaction under phase transition catalyst conditions to obtain the asymmetric divinylbenzyl fluorene.

[0025] Preferably, the basic reagent comprises an alkali metal hydroxide and / or an alkali metal alkoxide, and

[0026] The polymerization inhibitor 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-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide, and

[0027] The above phase transition catalyst comprises one or more of a quaternary ammonium salt, a quaternary phosphonium salt, and polyethylene glycol, and

[0028] The mass of the above phase transition catalyst is 5 to 25% of the mass of fluorene, and

[0029] The molar ratio of the above fluorene to the basic reagent is 1:1.8 to 5, and

[0030] The molar ratio of the above 2-vinylbenzyl chloride and 4-vinylbenzyl chloride is 2~6:4~8, and

[0031] The total moles of the above 2-vinylbenzyl chloride and 4-vinylbenzyl chloride and the molar ratio of fluorene is 1.8 to 2.2:1.

[0032] Preferably, under the above phase transition catalyst conditions, the temperature of the nucleophilic substitution reaction is 25 to 75°C, and the time is 8 to 18 hours.

[0033] The present invention also provides a thermosetting resin, comprising a thermosetting hydrocarbon resin and / or a thermosetting crosslinked resin, wherein the thermosetting hydrocarbon resin comprises a thermosetting hydrocarbon resin manufactured using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene as a raw material and / or a thermosetting hydrocarbon resin manufactured using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and 9,9'-bis(4-vinylbenzyl)-9H-fluorene as raw materials.

[0034] The above-mentioned thermosetting crosslinked resin comprises a thermosetting crosslinked resin obtained using a crosslinking agent and a terminal alkenyl polyphenylene ether as raw materials, wherein the crosslinking agent comprises 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and / or 9,9'-bis(4-vinylbenzyl)-9H-fluorene, and the terminal alkenyl polyphenylene ether has a structure shown in any one of Formulas 2 to 5.

[0035] Equation 2

[0037] Equation 3

[0038] Equation 4

[0039] Equation 5

[0040] The above 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene is the asymmetric divinylbenzyl fluorene described in the above technical plan, or the asymmetric divinylbenzyl fluorene produced by the manufacturing method described in the above technical plan.

[0041] The present invention also provided a method for manufacturing a thermosetting resin as described in the above technical plan, and

[0042] A step of obtaining a mixed solution by dissolving the manufacturing raw material and the initiator in toluene, and

[0043] The method includes the step of obtaining the thermosetting resin by removing toluene from the above mixed solution and then melt-thermally curing it.

[0044] The present invention also provides an application of the thermosetting resin described in the above technical plan or the thermosetting resin produced by the manufacturing method described in the above technical plan as a resin material used as a resin material for high-frequency high-speed substrates. Effects of the invention

[0045] The present invention provides an asymmetric divinylbenzyl fluorene having a structure represented by Chemical Formula 1, and Formula 1, the thermal analysis melting endothermic peak of the above 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene is 169~175°C, it has a monoclinic system, and the space group is P21 / c. The divinylbenzyl fluorene (9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF)) provided in the present invention is a nonpolar all-hydrocarbon compound having an asymmetric structure, and at the same time, since two asymmetric substituents at the 9-position of fluorene form a rigid cardo structure, the thermosetting resin prepared using the asymmetric divinylbenzyl fluorene provided in the present invention as a raw material has the characteristics of having a small dielectric loss tangent, a low dielectric constant, a high glass transition temperature, and easy processing, and can be used as a resin material for high-frequency high-speed substrates. Brief explanation of the drawing

[0046] Figure 1 is a schematic diagram showing the process of synthesizing asymmetric divinylbenzyl fluorene by a nucleophilic substitution reaction. Figure 2 is the HPLC spectrum of o, p-BVBF prepared in Example 1. FIG. 3 is of the o, p-BVBF prepared in Example 1. 1 This is the H NMR spectrum. Figure 4 shows the o, p-BVBF prepared in Example 1. 13 This is the C NMR spectrum. Figure 5 is the thermal analysis DSC spectrum of o, p-BVBF prepared in Example 1. Figure 6 is a single crystal structure diagram of o, p-BVBF prepared in Example 1. Figure 7 is a stacking diagram of the crystal cell of o, p-BVBF prepared in Example 1. Specific details for implementing the invention

[0047] The present invention synthesized an asymmetric divinylbenzyl fluorene, which is 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o,p-BVBF) having a structure represented by Chemical Formula 1, and

[0049] Equation 1

[0050] The above 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene has a thermal analysis melting endothermic peak of 169–175°C, has a monoclinic system, and its space group is P21 / c.

[0051] In the present invention, "asymmetric" in "asymmetric divinylbenzyl fluorene" means that there is another substituent at the 9th position of the fluorene group.

[0052] As one specific embodiment of the present invention, the thermal analysis melting endothermic peak of the 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene is 169~175℃ and can be 171~173℃, and the asymmetric divinylbenzyl fluorene can have a purity (HPLC) > 98.5%.

[0053] The present invention synthesized the above 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF) using two methods.

[0054] The present invention also provided a first method for producing asymmetric divinylbenzyl fluorene as described in the above technical plan, and

[0055] A step of obtaining a fluorene-containing mixture system by mixing fluorene, a basic reagent, a polymerization inhibitor, and a polar aprotic solvent, and

[0056] The method includes the step of obtaining the asymmetric divinylbenzyl fluorene by sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the mixture containing the fluorene, or by adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the mixture containing the fluorene to carry out a nucleophilic substitution reaction.

[0057] As a specific embodiment of the present invention, the basic reagent may include one or more of an alkali metal hydroxide, an alkali metal alkoxide, sodium hydride, and potassium hydride, and specifically, may be a mixture of an alkali metal hydroxide and an alkali metal alkoxide, an alkali metal hydroxide, an alkali metal alkoxide, sodium hydride, or potassium hydride, and the alkali metal hydroxide may be sodium hydroxide or potassium hydroxide, and the alkali metal alkoxide may be potassium tert-butoxide or sodium tert-butoxide, and the molar ratio of the fluorene to the basic reagent may be 1:1, 8 to 5, or 1:2 to 4.

[0058] As a specific embodiment of the present invention, the polymerization inhibitor may comprise 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 nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide (701 polymerization inhibitor), and specifically, 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, It may be 6-tetramethylpiperidine nitrogen oxide or 701 polymerization inhibitor, and the amount of the polymerization inhibitor may be 0.01 to 0.5% and 0.1 to 0.4% of the mass of vinylbenzyl chloride, and the vinylbenzyl chloride is 2-vinylbenzyl chloride and 4-vinylbenzyl chloride.

[0059] As a specific embodiment of the present invention, the polar aprotic solvent may include dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, or hexamethylphosphoramide, and the present invention has no particular limitation on the amount of the polar aprotic solvent used as long as the material can be uniformly mixed.

[0060] The present invention has no special requirements for the mixture of the fluorene, basic reagent, polymerization inhibitor, and polar aprotic solvent as long as they can be uniformly mixed.

[0061] The present invention provides a method in which 2-vinylbenzyl chloride is first added dropwise to the fluorene-containing mixed system to produce a single-substituted 9-(2-vinylbenzyl)fluorene intermediate, and then 4-vinylbenzyl chloride is added dropwise to react, thereby significantly improving the yield of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o, p-BVBF) compared to the method of simultaneously adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise. Furthermore, if 4-vinylbenzyl chloride is added dropwise first and then 2-vinylbenzyl chloride is added to react, mainly 9,9'-bis-(4-vinylbenzyl)fluorene (p, p-BVBF) is obtained, whereas 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o, The yield of p-BVBF is very low, which is because the steric hindrance of 2-vinylbenzyl chloride is much greater than that of 4-vinylbenzyl chloride during the reaction process, and it is difficult to introduce a 2-vinylbenzyl group when a 4-vinylbenzyl group is already present at the 9 position of the fluorene group.

[0062] As a specific embodiment of the present invention, the molar ratio of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride may be 2 to 6:4 to 8, specifically 2:8, 3:7, 4:6, 5:5, or 6:4, and the molar ratio of the total moles of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to fluorene may be 1.8 to 2.2:1, specifically 2:1.

[0063] In a specific embodiment of the present invention, the nucleophilic substitution reaction temperature may be 20 to 50°C or 30 to 40°C, and the nucleophilic substitution reaction time may be 2 to 8 hours or 3 to 7 hours. In a specific embodiment of the present invention, the nucleophilic substitution reaction may be performed under stirring conditions. The present invention has no particular limitations regarding the stirring.

[0064] As a specific embodiment of the present invention, the following step after the nucleophilic substitution reaction may be further included:

[0065] After the above nucleophilic substitution reaction, the system is mixed with ice water, and then solid-liquid separation is performed to obtain a solid, and

[0066] After washing the above solid with water, the asymmetric divinylbenzyl fluorene is obtained by sequentially pulping, filtration, recrystallization, and drying.

[0067] As a specific embodiment of the present invention, the volume ratio of the system to the ice water after the nucleophilic substitution reaction may be 3:8 to 12 or 3:10 to 11, and the solid-liquid separation may be filtration. The present invention has no particular limitation on the number of washes as long as the pH value of the filtrate after washing is neutral. As a specific embodiment of the present invention, the pulping solvent may be an alcohol solvent, and the alcohol solvent may include methanol, ethanol, or isopropanol. The pulping temperature may be 0 to 40°C or 10 to 30°C. The present invention has no particular limitation on the filtration and may adopt general methods in the field. As a specific embodiment of the present invention, the recrystallization solvent may include toluene, ethylbenzene, xylene, or isopropylbenzene, the drying may be vacuum drying, the temperature of the vacuum drying may be 70 to 90°C or 75 to 80°C, and the present invention has no particular limitation on the vacuum drying time, as long as the solvent can be removed.

[0068] The present invention also provided a second method for producing asymmetric divinylbenzyl fluorene as described in the above technical plan, and

[0069] A step of obtaining a phase transition catalyst system containing fluorene by mixing fluorene, a basic reagent, a polymerization inhibitor, a phase transition catalyst, and a solvent, and

[0070] The method includes the step of sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the fluorene-containing phase transition catalyst system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the fluorene-containing phase transition catalyst system to carry out a nucleophilic substitution reaction under phase transition catalyst conditions to obtain the asymmetric divinylbenzyl fluorene.

[0071] As a specific embodiment of the present invention, the basic reagent may include an alkali metal hydroxide and / or an alkali metal alkoxide, and specifically, may be a mixture of an alkali metal hydroxide and an alkali metal alkoxide, an alkali metal hydroxide, or an alkali metal alkoxide, and the alkali metal hydroxide may be sodium hydroxide or potassium hydroxide, and the alkali metal alkoxide may be potassium tert-butoxide or sodium tert-butoxide, and the molar ratio of the fluorene to the basic reagent may be 1:1, 8 to 5, or 1:2 to 4.

[0072] As a specific embodiment of the present invention, the polymerization inhibitor may comprise 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 nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide (701 polymerization inhibitor), and specifically, 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, It may be 6-tetramethylpiperidine nitrogen oxide or 701 polymerization inhibitor, and the amount of the polymerization inhibitor used may be 0.01 to 0.5% of the mass of vinylbenzyl chloride, and may also be 0.1 to 0.4%, and the vinylbenzyl chloride is 2-vinylbenzyl chloride and 4-vinylbenzyl chloride.

[0073] As a specific embodiment of the present invention, the phase transition catalyst may comprise one or more of a quaternary ammonium salt, a quaternary phosphonium salt, and polyethylene glycol, and specifically may be a quaternary ammonium salt, a quaternary phosphonium salt, or polyethylene glycol, wherein the quaternary ammonium salt may be tetrabutyl bromide ammonium (TBAB), tetrabutyl chloride ammonium (TBAC), benzyl triethyl bromide ammonium (BTEAB), benzyl triethyl chloride ammonium (BTEAC), hexadecyl triethyl bromide ammonium (HTEAB) or hexadecyl triethyl chloride ammonium (HTEAC), etc., and the quaternary phosphonium salt may be hexadecyl tributyl bromide phosphonium (HTBPB), hexadecyl tributyl chloride phosphonium (HTBPC), tetrabutyl bromide phosphonium (TBPB), It may be tetrabutyl chloride phosphonium (TBPC), tetraphenyl bromide phosphonium (TPPB), or tetraphenyl chloride phosphonium (TPPC), and the polyethylene glycol may be PEG-400, PEG-600, or PEG-800. In a specific embodiment of the present invention, the mass of the phase transition catalyst may be 5 to 25% of the mass of fluorene, and may be 10 to 20%.

[0074] As a specific embodiment of the present invention, the nucleophilic substitution reaction under the phase transition catalyst conditions may be a nucleophilic substitution reaction under liquid-liquid phase transition catalyst conditions or a nucleophilic substitution reaction under solid-liquid phase transition catalyst conditions.

[0075] As a specific embodiment of the present invention, when the nucleophilic substitution reaction under the phase transition catalyst conditions is a reaction under solid-liquid phase transition catalyst conditions, the solvent may be an organic solvent, and the organic solvent may include dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, or hexamethylphosphoramide.

[0076] As a specific embodiment of the present invention, when the nucleophilic substitution reaction under the phase transition catalyst condition is a reaction under the liquid-liquid phase transition catalyst condition, the solvent may be a mixture of an aromatic hydrocarbon and water or a mixture of an alkane and water, the aromatic hydrocarbon may be toluene, xylene, ethylbenzene, or isopropylbenzene, and the alkane may be n-hexane, n-heptane, cyclohexane, methylcyclopentane, or petroleum ether.

[0077] The present invention first produces a single-substituted 9-(2-vinylbenzyl)fluorene intermediate by adding 2-vinylbenzyl chloride dropwise, and then reacts by adding 4-vinylbenzyl chloride dropwise. Compared to the case where a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride is directly added dropwise, the yield of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o, p-BVBF) is significantly improved. If 2-vinylbenzyl chloride is added dropwise after adding 4-vinylbenzyl chloride and reacted, mainly 9,9'-bis-(4-vinylbenzyl)fluorene (p, p-BVBF) is obtained, and the yield of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o, p-BVBF) is very low. This is because the steric hindrance of 2-vinylbenzyl chloride in the reaction is much greater than that of 4-vinylbenzyl chloride, and if a 4-vinylbenzyl group has already been introduced at the 9-position of fluorene, it becomes difficult to introduce a 2-vinylbenzyl group. Therefore, if 2-vinylbenzyl chloride is added dropwise first and reacted for a certain period of time, and then 4-vinylbenzyl chloride is added dropwise and reacted, the yield of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF) is improved.

[0078] As a specific embodiment of the present invention, the molar ratio of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride may be 2 to 6:4 to 8, specifically 2:8, 3:7, 4:6, 5:5, or 6:4, and the molar ratio of the total moles of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the moles of fluorene may be 1.8 to 2.2:1, specifically 2:1.

[0079] In a specific embodiment of the present invention, the temperature of the nucleophilic substitution reaction under the phase transition catalyst conditions may be 25 to 75°C or 30 to 70°C, and the time of the nucleophilic substitution reaction under the phase transition catalyst conditions may be 8 to 18 hours or 10 to 15 hours. In a specific embodiment of the present invention, the reaction under the phase transition catalyst conditions must be carried out under good stirring conditions.

[0080] As a specific embodiment of the present invention, the following step may be further included after the nucleophilic substitution reaction under the phase transition catalyst conditions.

[0081] After the nucleophilic substitution reaction under the above phase transition catalyst conditions, the system is subjected to solvent removal by distillation, followed by extraction with the addition of water and toluene to obtain the organic phase, and

[0082] After concentrating the above organic phase, the asymmetric divinylbenzyl fluorene is obtained by sequentially undergoing washing, pulping, filtration, recrystallization, and drying processes.

[0083] In a specific embodiment of the present invention, the volume ratio of water to toluene used for extraction may be 1:0.8 to 1:2 or 1:1, and the concentration may be performed by vacuum distillation; the present invention has no specific requirement for vacuum distillation as long as the solvent can be removed. In a specific embodiment of the present invention, the washing solvent may be a saturated ammonium chloride solution, and the present invention has no specific requirement for the number of washes as long as the pH value of the washing solution after washing is neutral. In a specific embodiment of the present invention, the solvent used for pulping may be an alcohol solvent with five or fewer carbon atoms, and the alcohol solvent with five or fewer carbon atoms may include methanol, ethanol, or isopropanol; and the temperature of the pulping may be 0 to 40°C or 10 to 30°C. The present invention has no specific limitations on the filtration, and general methods in the field may be adopted. As a specific embodiment of the present invention, the recrystallization solvent may include toluene, ethylbenzene, xylene, or isopropylbenzene, the drying may be vacuum drying, the temperature of the vacuum drying may be 70 to 90°C or 75 to 80°C, and the present invention has no particular limitation on the vacuum drying time, as long as the solvent can be removed.

[0084] Figure 1 is a schematic diagram showing the process of synthesizing asymmetric divinylbenzyl fluorene through a nucleophilic substitution reaction.

[0085] The present invention also provides a thermosetting resin, comprising a thermosetting hydrocarbon resin and / or a thermosetting crosslinked resin, wherein the thermosetting hydrocarbon resin comprises a thermosetting hydrocarbon resin manufactured using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene as a raw material and / or a thermosetting hydrocarbon resin manufactured using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and 9,9'-bis(4-vinylbenzyl)-9H-fluorene as raw materials.

[0086] The above-mentioned thermosetting crosslinked resin comprises a thermosetting crosslinked resin obtained using a crosslinking agent and a terminal alkenyl polyphenylene ether as raw materials, wherein the crosslinking agent comprises 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and / or 9,9'-bis(4-vinylbenzyl)-9H-fluorene, and the terminal alkenyl polyphenylene ether has a structure shown in any one of Formulas 2 to 5.

[0087] Equation 2

[0088] Equation 3

[0089] Equation 4

[0090] Equation 5

[0091] The above 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene is the asymmetric divinylbenzyl fluorene described in the above technical plan, or the asymmetric divinylbenzyl fluorene prepared by the method described in the above technical plan.

[0092] As a specific embodiment of the present invention, a thermosetting hydrocarbon resin produced using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene as a raw material has a low dielectric constant (Dk(10GH)2.8), a low dielectric loss tangent (Df(10GH)0.00030), and a high glass transition temperature (Tg 360℃).

[0093] As a specific embodiment of the present invention, among the raw materials for manufacturing a thermosetting hydrocarbon resin manufactured using the 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and 9,9'-bis(4-vinylbenzyl)-9H-fluorene, the molar percentage of o,p-BVF among 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVF) and 9,9'-bis(4-vinylbenzyl)-9H-fluorene (p,p-BVBF) may be 10~60% and may be 25~50%. In the present invention, the 9,9'-bis(4-vinylbenzyl)-9H-fluorene is a symmetric divinylbenzyl fluorene, where "symmetry" means that there is an identical substituent at the 9th position of the fluorene group, and the structural formula of the 9,9'-bis(4-vinylbenzyl)-9H-fluorene is as follows.

[0094]

[0095] As a specific embodiment of the present invention, a thermosetting hydrocarbon resin prepared using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and 9,9'-bis(4-vinylbenzyl)-9H-fluorene as raw materials has the characteristics of a very low dielectric constant, a very low dielectric loss tangent, and a significantly high glass transition temperature. For example, when the molar ratio of o, p-BVF and p, p-BVBF is 1:1, the dielectric constant of the obtained thermosetting hydrocarbon resin is Dk(10GH)2.8, the dielectric loss tangent is Df(10GH)0.00042, and the glass transition temperature is 352℃.

[0096] As a specific embodiment of the present invention, the number average molecular weight (Mn) of the terminal alkenyl polyphenylene ether in the thermosetting crosslinked resin prepared using a crosslinking agent and a terminal alkenyl polyphenylene ether as raw materials may be 1800 to 2300, and the terminal alkenyl polyphenylene ether may specifically be a terminal vinylbenzyl modified polyphenylene ether, and the structural formula of the terminal vinylbenzyl modified polyphenylene ether is as follows.

[0097]

[0098] As a specific embodiment of the present invention, the method for manufacturing the terminal vinylbenzyl modified polyphenylene ether may include the following steps.

[0099] Hydroxy polyphenylene ether is obtained by oxidative bond copolymerization reaction of 2,6-dimethylphenol, divalent phenol, and a catalyst in an oxygen atmosphere, and

[0100] The above hydroxy polyphenylene ether and vinylbenzyl chloride are reacted under phase transition conditions and then precipitated with methanol to obtain the above terminal vinylbenzyl modified polyphenylene ether.

[0101] As a specific embodiment of the present invention, the catalyst comprises a copper amine complex catalyst, wherein the copper amine complex catalyst comprises N, N'-tetra-tert-butylethylenediamine, N-methylbutylamine, copper(I) bromide, copper(I) chloride, copper chloride, and copper bromide, and the number average molecular weight of the hydroxy polyphenylene ether may be 1600 to 2000.

[0102] As a specific embodiment of the present invention, when a thermosetting crosslinked resin is manufactured using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and 9,9'-bis(4-vinylbenzyl)-9H-fluorene as crosslinking agents, the mass percentage of the crosslinking agent in the manufacturing raw materials may be 10-50% or 20-40%, and the molar percentage of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o, p-BVF) among the crosslinking agents may be 10-60% or 25-50%.

[0103] The thermosetting resin provided in the present invention has a low dielectric constant and a low dielectric loss tangent, while also having an improved glass transition temperature, thus having good application prospects as a resin material for high-frequency substrates.

[0104] The present invention also provides a method for manufacturing a thermosetting resin according to the above technical method, comprising the following steps.

[0105] A mixed solution is obtained by dissolving the manufacturing raw materials and the initiator in toluene, and

[0106] After removing toluene from the above mixed solution, the thermosetting resin is obtained by melting and heat-curing.

[0107] As a specific embodiment of the present invention, the initiator may comprise a peroxide, wherein the peroxide is di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxybenzoate, di(tert-butyl peroxy)isopropylbenzene, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, dilauroyl peroxide, 1,1-di(tert-butyl peroxy)cyclohexane, 1,1-di(tert-butyl peroxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, 3,3,5,7,7-pentamethyl-1,2,4-trioxane (T311), tert-butyl peroxy-2-ethylhexanoate It may include tert-butyl peroxy-2-hexylhexane carbonate, and the mass ratio of the manufacturing raw material to the initiator may be 1:0.001 to 0.008, and may also be 1:0.003 to 0.005.

[0108] As a specific embodiment of the present invention, the method of removing toluene from the mixed solution may be vacuum distillation.

[0109] As a specific embodiment of the present invention, the melt heat curing temperature may be 200 to 240°C or 210 to 230°C, the melt heat curing pressure may be 70 to 80 mmHg or 75 to 78 mmHg, and the melt heat curing time may be 80 to 120 minutes or 90 to 110 minutes.

[0110] The present invention also provides an application for using a thermosetting resin described in the above technical plan or a thermosetting resin manufactured by the manufacturing method described in the above technical plan as a resin material for a high-frequency high-speed substrate.

[0111] To further explain the present invention, the technical solution provided by the present invention is described in detail below together with the embodiments, but this should not be understood as a limitation on the scope of protection of the present invention.

[0112] The analytical equipment and analytical test methods used in the examples are as follows:

[0113] 1. Purity measurement method (HPLC): Agilent 1260 high-pressure liquid chromatograph, USA, column: Kromasil 100-5 C18 250cm x 4.6mm, mobile phase acetonitrile / methanol volume ratio = 9:1, flow rate 0.8mL / min, detection wavelength 254nm, injection volume 2μL, pump mode is binary high-pressure gradient.

[0114] 2. Thermal analysis method: DSC was measured using a Pyris1 thermal analyzer (Perkin Elemer), the heating range was 50 to 200°C, and the heating rate was 10°C / min.

[0115] 3. Nuclear Magnetic Resonance Spectroscopy: Bruker AV 400 nuclear magnetic resonance apparatus, DMSO-d6 as solvent, and TMS as internal standard are used.

[0116] 4. Measurement of single crystal structure: Measure using a Bruker D8 Venture single crystal diffractometer, JY / T0588-2020, according to the general rules of molecular structure analysis.

[0117] 5. Measurement of dielectric constant Dk (10GHz) and dielectric loss tangent Df (10GHz): Resin sheets of 80mm x 80mm x 0.4mm are fabricated by the molten sample casting method (thermal curing conditions: temperature is 220℃, pressure is 70~80mmHg, and time is 100 min), and measurements are taken at a frequency of 10GHz using an American Angelent N5230A vector network analyzer (SPDR).

[0118] 6. Measurement of polymer molecular weight: An Angelent 1260 gel permeation chromatograph (GPC) is used with tetrahydrofuran as the mobile phase and polystyrene as the standard sample.

[0119] 7. Measurement of polymer glass transition temperature: Measured using a Perkin Elmer Differential Scanning Calorimeter dsc 4000.

[0120] 2-vinylbenzyl chloride (HPLC purity 99.0%), 4-vinylbenzyl chloride (HPLC purity 99.5%), and 1,2-bis(4-vinylphenyl)ethane (BVPE) (HPLC purity 99.5%) in the examples were all produced by Shandong Xingshun New Materials Co., Ltd.

[0121] Examples 1 to 7 prepared 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF), and Examples 8 to 13 prepared thermosetting resins.

[0122] Example 1

[0123] 300 mL of dimethyl sulfoxide anhydrous, 1.10 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor were added to a reaction flask and stirred for 30 minutes under a nitrogen stream, then 0.5 mol of fluorene was added and stirred to dissolve, then 0.4 mol of 2-chloromethylstyrene was added dropwise and reacted for 1.0 hours at 30–35°C under stirring conditions of 350 r / min, and then 0.4 mol of 4-chloromethylstyrene 6 mol was added dropwise while stirring and the reaction was continued for 2.5 hours. After the reaction, the solution was slowly added to 1000 mL of ice water, the precipitated solid was filtered, the filtrate was washed with water until neutral, the solid was pulped twice with 500 mL of methanol (at 30°C), the solid obtained by filtration was recrystallized twice with toluene, and the obtained solid was vacuum dried at 80°C until the weight became constant to obtain 144.5 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF), and the yield was 72.5%.

[0124] o, p-BVBF is a white crystal, and the prepared o, p-BVBF was detected by high-performance liquid chromatography to obtain a high-performance liquid chromatography spectrum. As shown in Figure 2, Table 1 is the high-performance liquid chromatography peak information, and according to the high-performance liquid chromatography detection results, the HPLC purity of o, p-BVBF was 99.15%.

[0125] Nuclear magnetic resonance detection was performed on the synthesized o, p-BVBF, and 1 H NMR spectrum and 13 3 C NMR spectra were obtained, and as shown in Figures 3 and 4, Figure 3 is of o, p-BVBF 1 This is the H NMR spectrum, and Figure 4 is of o, p-BVBF 13 This is the C NMR spectrum.

[0126] 1¹H NMR (400 MHz, DMSO-d6) δ: 3.43(s, 2H, CH2), 3.54(s, 2H, CH2), 5.03-5.08(m, 2H, 2X alkene hydrogen), 5.40-5.59(m, 2H, 2X alkene hydrogen), 6.40-6.42(m, ¹H, ¹X alkene hydrogen), 6.49(d, 2H, ²X benzene ring hydrogen), 6.70-6.77(m, 2H, ²X benzene ring hydrogen), 6.97-7.01(m, ³H, ²X benzene ring hydrogen, ¹X alkene hydrogen), 6.87-6.01. 95(m, 1H, 1X benzene ring hydrogen), 7.05-7.20(m, 4H, 4X fluorene ring hydrogen), 7.22-7.25(m, 1H, 1X benzene ring hydrogen), 7.33-7.58(m, 4H, 4X fluorene ring hydrogen).

[0127] 13 13C NMR (100 MHz, DMSO-d6)δ: 40.9(CH2), 43.3(CH2), 56.7(9-fluorene C), 113.2, 115.0, 119.7, 124.7, 124.9, 125.3, 126.3, 126.5, 126.7, 127.1, 129.9, 130.9, 134.3, 134.9, 135.1, 136.3, 136.9, 137.0, 140.3, 148.0(benzene ring C, fluorene ring C, vinyl C).

[0128] 1 H NMR spectrum and 13 The C NMR spectrum is in perfect agreement with the structure of o, p-BVBF.

[0129] The prepared o, p-BVBF was detected using a Pyris1 thermal analyzer, and the obtained DSC spectrum is shown in Fig. 5. From Fig. 5, it can be seen that the melting point of o, p-BVBF is 171.4 to 172.7°C.

[0130] Figure 6 is a single crystal structure diagram of o, p-BVBF, and in the figure represents an H atom, and Fig. 7 is a stacking diagram of the unit cell of o, p-BVBF. The crystallographic parameters of o, p-BVBF are shown in Table 2, and the bond length and bond angle data of o, p-BVBF are as shown in Table 3, and the molecular structure of o, p-BVBF was further confirmed through single crystal structure measurement results.

[0131] HPLC peak information of o, p-BVBF peak Duration / minute category Peak area Peak height / mV Peak Area / % 1 4. 135 VB 0. 2405 308 0. 011 2 4. 370 VB 0. 9071 1311 0. 050 3 4. 526 BV 0. 3897 555 0. 021 4 5. 262 VV 10. 5175 13630 0. 577 5 5. 561 VB 1808. 5450 2374847 99. 150 6 6. 509 VB 0. 1061 131 0. 006 7 7. 548 BB 0. 8422 708 0. 046

[0133] Crystallographic parameters of o, p-BVBF compound o, p -BVBF molecular formula C 31 H 26 molecular weight 398. 52 Test temperature 223. 00 K wavelength 1. 54178 Å Crystal system monoclinic system Space group P21 / c Lattice constant a=10.7721(4)Å =90° b=10. 7089(4)Å =101. 173(2)°. c=19. 7979(8)Å=90° Unit cell volume 2240. 55(15) Å 3 Z 4 density 1. 181 megagrams / cubic meter absorption coefficient 0. 501mm -1 F(000) 848. 0 Decision size 0. 15X0. 13X0. 10mm 3 Angle range 4. 183~68. 278° Indicator range -11<=h<=12, -12<=k<=11, -22<=l<=23 Number of collected diffraction points 18475 Number of independent diffraction points 4058[R(int)=0.0467] =68.278° completeness 99. 2% Absorption correction Semi-empirical from equivalents Maximum transmittance and minimum transmittance 0.753 and 0.639 Purification method Full-matrix least-squares on F 2 Number of data points / Number of added limits / Number of refined parameters 4058 / 0 / 280 GooF value 1. 061 Deviation coefficient [I > 2 sigma(I)] R 1=0. 0401, wR 2=0. 1054 Deviation coefficient (all data) R 1=0. 0547, wR 2=0. 1128 Residual electron cloud density 0.15 and -0.19e. Å -3

[0135] o, bond length [Å] and bond angle [°] of p-BVBF C (1)-C (6) 1. 387(2) C (6)-C (5)-C (9) 119. 26(13) C (2)-C (3) 1. 372(2) C (1)-C (6)-C (5) 121. 67(14) C (3)-C (4) 1. 3994(19) C (8)-C (7)-C (4) 127. 53(15) C (4)-C (5) 1. 4061(19) C (5)-C (9)-C (10) 116. 23(10) C (4)-C (7) 1. 478(2) C (11)-C (10)-C (9) 110. 07(10) C (5)-C (6) 1. 3906(19) C (20)-C (10)-C (9) 112. 41(10) C (5)-C (9) 1. 5124(17) C (20)-C (10)-C (11) 112. 22(10) C (7)-C (8) 1. 306(2) C (26)-C (10)-C (9) 108. 04(10) C (9)-C (10) 1. 5679(17) C (26)-C (10)-C (11) 112. 23(10) C (10)-C (11) 1. 5473(17) C (26)-C (10)-C (20) 101. 57(10) C (10)-C (20) 1. 5203(17) C (12)-C (11)-C (10) 114. 30(10) C (10)-C (26) 1. 5203(16) C (13)-C (12)-C (11) 120. 89(12) C (11)-C (12) 1. 5085(18) C (13)-C (12)-C (17) 117. 43(13) C (12)-C (13) 1. 3880(18) C (17)-C (12)-C (11) 121. 68(12) C (12)-C (17) 1. 390(2) C (14)-C (13)-C (12) 121. 35(14) C (13)-C (14) 1. 384(2) C (13)-C (14)-C (15) 121. 19(13) C (14)-C (15) 1. 385(2) C (14)-C (15)-C (16) 117. 77(14) C (15)-C (16) 1. 396(2) C (14)-C (15)-C (18) 119. 89(14) C (15)-C (18) 1. 471(2) C (16)-C (15)-C (18) 122. 34(15) C (16)-C (17) 1. 384(2) C (17)-C (16)-C (15) 120. 77(14) C (18)-C (19) 1. 284(3) C (16)-C (17)-C (12) 121. 48(13) C (20)-C (21) 1. 3927(19) C (19)-C (18)-C (15) 127. 95(19) C (20)-C (25) 1. 3886(18) C (21)-C (20)-C (10) 110. 43(11) C (21)-C (22) 1. 386(2) C (25)-C (20)-C (10) 129. 29(12) C (21)-C (27) 1. 4690(18) C (25)-C (20)-C (21) 120. 27(12) C (22)-C (23) 1. 387(3) C (20)-C (21)-C (27) 108. 87(11) C (23)-C (24) 1. 381(3) C (22)-C (21)-C (20) 120. 55(13) C (24)-C (25) 1. 383(2) C (22)-C (21)-C (27) 130. 58(14) C (26)-C (27) 1. 3945(17) C (21)-C (22)-C (23) 118. 61(16) C (26)-C (31) 1. 3818(18) C (24)-C (23)-C (22) 120. 92(15) C (27)-C (28) 1. 3870(19) C (23)-C (24)-C (25) 120. 61(15) C (28)-C (29) 1. 379(2) C (24)-C (25)-C (20) 118. 95(14) C (29)-C (30) 1. 384(2) C (27)-C (26)-C (10) 110. 77(10) C (30)-C (31) 1. 3887(19) C (31)-C (26)-C (10) 128. 93(11) C (31)-C (26)-C (27) 120. 29(12) C (2)-C (1)-C (6) 119. 74(14) C (26)-C (27)-C (21) 108. 23(11) C (3)-C (2)-C (1) 119. 58(13) C (28)-C (27)-C (21) 131. 19(12) C (2)-C (3)-C (4) 121. 93(14) C (28)-C (27)-C (26) 120. 56(12) C (3)-C (4)-C (5) 118. 60(13) C (29)-C (28)-C (27) 118. 83(13) C (3)-C (4)-C (7) 119. 52(13) C (28)-C (29)-C (30) 120. 79(13) C (5)-C (4)-C (7) 121. 88(12) C (29)-C (30)-C (31) 120. 63(13) C (4)-C (5)-C (9) 122. 26(12) C (26)-C (31)-C (30) 118. 88(13)

[0137] Example 2

[0138] 300 mL of dimethyl sulfoxide anhydrous, 1.10 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor were added to a reaction flask and stirred for 30 minutes under a nitrogen stream, then 0.5 mol of fluorene was added and dissolved by stirring, then 0.3 mol of 2-chloromethylstyrene was added dropwise and reacted for 1.0 hours at 35°C under stirring conditions of 350 r / min, and then 0.4-chloromethylstyrene 7 mol was added dropwise while stirring, and the reaction was continued with stirring for 2.5 hours. After the reaction, the solution was slowly added to 1000 mL of ice water, the precipitated solid was filtered, the filtrate was washed with water until neutral, the solid was pulped twice with 500 mL of methanol (at 30°C), the filtered solid was recrystallized twice with toluene, and the obtained solid was vacuum dried at 80°C until the weight became constant to obtain 110.8 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF), which is a white crystal, with a purity (HPLC) of 99.1% and a yield of 55.6%.

[0139] Example 3

[0140] 300 mL of dimethyl sulfoxide anhydrous, 1.10 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor were added to a reaction flask and stirred for 30 minutes under a nitrogen stream; then, 0.5 mol of fluorene was added and stirred to dissolve; subsequently, 0.5 mol of 2-chloromethylstyrene was added dropwise and reacted for 1.0 hours at 35°C under stirring conditions of 350 r / min; and then 0.4-chloromethylstyrene 5 mol was added dropwise while stirring, and the reaction was continued with stirring for 5 hours. After the reaction, the solution was slowly added to 1000 mL of ice water, the precipitated solid was filtered, the filtrate was washed with water until neutral, the solid was pulped twice with 500 mL of methanol (at 30°C), the filtered solid was recrystallized twice with toluene, and the obtained solid was vacuum dried at 80°C until the weight became constant to obtain 126.7 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF), which is a white crystal, with a purity (HPLC) of 99.2% and a yield of 63.6%.

[0141] Example 4

[0142] 300 mL of anhydrous dimethyl sulfoxide, 1.10 mol of tert-butoxide potassium, and 0.3 g of 701 polymerization inhibitor were added to a reaction flask and stirred for 30 minutes under a nitrogen stream; then, 0.5 mol of fluorene was added and stirred to dissolve; subsequently, a mixed solution of 0.4 mol of 2-chloromethylstyrene and 0.6 mol of 4-chloromethylstyrene was added dropwise; the mixture was reacted for 3.5 hours at 35°C under stirring conditions of 350 r / min; after the reaction, the solution was slowly added to 1000 mL of ice water; the precipitated solid was filtered and washed with water until the filtrate became neutral; the solid was pulped twice with 500 mL of methanol (at 30°C); the filtered solid was recrystallized twice with toluene; and the obtained solid was vacuum dried at 80°C until the weight became constant. 6 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF) was obtained, which is a white crystal, has a purity (HPLC) of 98.5%, and a yield of 45.5%.

[0143] Example 5

[0144] 500 mL of toluene and 0.5 mol of fluorene were added to a reaction flask and dissolved by stirring; while stirring, 180 g of a pre-prepared 50% sodium hydroxide solution was added, 8.5 g of tetrabutyl bromide ammonium (TBAB) and 0.3 g of 701 polymerization inhibitor were added, and 0.4 mol of 2-chloromethylstyrene was added dropwise while stirring under a nitrogen stream at 40°C, and the reaction was carried out for 4.0 hours under stirring conditions of 350 r / min, and then 0.4 mol of 4-chloromethylstyrene was added while stirring. 6 mol was added dropwise and the reaction was continued with stirring for 10 hours, cooled to room temperature, and 500 mL of water was slowly added while stirring to separate the organic phase, washed twice with water using 500 mL of water each time, washed the organic phase with 500 mL of saturated aqueous ammonium chloride solution, washed with water until neutral, separated the organic phase, and removed toluene by distillation under reduced pressure. The solid was pulped twice with 500 mL of methanol (at 30°C), and the solid obtained by filtration was recrystallized twice with toluene. The obtained solid was vacuum dried under conditions of 80°C until the weight became constant to obtain 124.3 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF), which is a white crystal, has a purity (HPLC) of 98.5%, and a yield of 62.4%.

[0145] Example 6

[0146] 500 mL of toluene and 0.5 mol of fluorene were added to a reaction flask and dissolved by stirring; while stirring, 180 g of a pre-prepared 50% sodium hydroxide solution was added, 8.5 g of tetrabutyl bromide ammonium (TBAB) and 0.3 g of 701 polymerization inhibitor were added, and while stirring under a nitrogen stream at 40°C, a mixed solution of 0.5 mol of 2-chloromethylstyrene and 0.5 mol of 4-chloromethylstyrene was added dropwise, and under stirring conditions of 350 r / min14. The mixture was reacted for 0 hours, cooled to room temperature, and slowly added 500 mL of water while stirring to separate the organic phase. The organic phase was washed twice with water, using 500 mL of water each time, and washed with 500 mL of saturated ammonium chloride aqueous solution until neutral. The organic phase was separated, and toluene was removed by distillation under reduced pressure. The solid was pulped twice with 500 mL of methanol (at 30°C), and the solid obtained by filtration was recrystallized twice with toluene. The obtained solid was vacuum dried under conditions of 80°C until the weight became constant to obtain 84.7 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF), which is a white crystal. The purity (HPLC) was 98.5%, and the yield was 42.5%.

[0147] Example 7

[0148] 500 mL of acetonitrile, 1.2 mol of potassium hydroxide powder, 30 g of PEG-400, and 0.3 g of 701 polymerization inhibitor were added to a reaction flask, and 0.5 mol (83 g) of fluorene was added while stirring, and 0.4 mol of 2-chloromethylstyrene was added dropwise under stirring at 40°C under a nitrogen stream, and the reaction was carried out for 4.0 hours under stirring conditions of 350 r / min, and then 0.4 mol of 4-chloromethylstyrene was added while stirring. 6 mol was added dropwise and stirred continuously for 8.0 hours, the reaction was stopped, and acetonitrile was removed by distillation. Then, 500 mL of water and 500 mL of toluene were added, the layers were separated, the organic phase was washed with 500 mL of saturated ammonium chloride solution, washed with water until neutral, and toluene was removed by distillation under reduced pressure. The solid was pulped twice with 500 mL of methanol (at 30°C), and the solid obtained by filtration was recrystallized twice with toluene. The obtained solid was vacuum dried at 80°C until the weight became constant to obtain 106.6 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF), which is a white crystal, has a purity (HPLC) of 98.7%, and a yield of 53.5%.

[0149] Example 8

[0150] 20 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF) prepared in Example 1 and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene, the solvent was removed under reduced pressure, and then a thermosetting hydrocarbon resin was prepared by melt injection (thermal curing conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), the glass transition temperature was measured, and the prepared resin was fabricated into 80 mm x 80 mm x 0.4 mm thin sections, and the dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0151] Example 9

[0152] 500 mL of acetonitrile, 1.4 mol of potassium tert-butoxide, 30 g of PEG-400, and 0.5 g of 701 polymerization inhibitor were added to a reaction flask, and 0.6 mol of fluorene and 1.4 mol of 4-vinylbenzyl chloride (HPLC, 99%) were added while stirring under a nitrogen stream. The reaction was carried out at 30–35°C and stirring at 350 r / min until the fluorene content analyzed by HPLC was less than 1 wt%, after which the reaction was stopped, the acetonitrile was removed by distillation, and 500 mL of water and 500 mL of toluene were added to separate the layers. The organic phase was washed with a saturated ammonium chloride solution, washed three times with water (500 mL of water per wash) until neutral, and the toluene was removed by distillation under reduced pressure, with a volume ratio of 1:0. A mixed solvent of 3 parts toluene and methanol was added and heated to completely dissolve, and crystallized by cooling at a constant temperature of 5°C at a rate of 0.5°C / min, followed by filtration; the obtained solid component was dried under conditions of 90°C until the weight became constant to obtain 9,9-bis(2-vinylbenzyl)-9H-fluorene (p, p-BVBF), which is a white crystal, has a melting point of 118.5–120.0°C, and a purity (HPLC) of 99.5%;

[0153] 20 g of 9,9-bis(4-vinylbenzyl)-9H-fluorene (p, p-BVBF) and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene, and after removing the solvent by reduced pressure, a thermosetting hydrocarbon resin was prepared by melt injection (thermal curing conditions: temperature 220°C, pressure 70–80 mmHg, time 100 min). The glass transition temperature was measured, and the prepared resin was fabricated into 80 mm x 80 mm x 0.4 mm thin sections. The dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0154] Example 10

[0155] 9,9-bis(2-vinylbenzyl)-9H-fluorene (p, p-BVBF) was prepared according to the method of Example 9, having a white crystal, a melting point of 118.5–120.0°C, and a purity (HPLC) of 99.5%.

[0156] 10 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF) prepared in Example 1, 10 g of 9,9-bis(4-vinylbenzyl)-9H-fluorene(p, p-BVBF) and T311 peroxide initiator 0. 1 g was dissolved in 50 g of toluene, and after removing the solvent by reduced pressure, a thermosetting hydrocarbon resin was prepared using the melt injection method (thermal curing conditions: temperature 220°C, pressure 70–80 mmHg, time 100 min). The glass transition temperature was measured, and the prepared resin was fabricated into 80 mm x 80 mm x 0.4 mm thin sections. The dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0157] Example 11

[0158] Add 150 mL of methanol, 0.09 mol of N,N-di-tert-butylethylenediamine, and 0.07 mol of copper bromide to a 2 L 4-necked bottle, stir and dissolve, then supply oxygen and continuously bubble while adjusting the temperature to 40–45°C and stirring to carry out the reaction. Dropwise, add a 500 ml toluene / 150 ml methanol mixed solution containing 1.0 mol of 2,6-dimethylphenol and 0.125 mol of tetramethylbisphenol A to the reaction flask. After the addition is complete, continue the reaction for 4 hours while continuously stirring at the same temperature and passing oxygen through continuously bubbling. Upon completion of the reaction, neutralize to neutral with 10% dilute hydrochloric acid, add 50 mL of an aqueous solution containing 7 g (0.04 mol) of EDTA-2Na, and stir for 30 minutes. Then, add 600 mL of methanol, and The precipitate was filtered, pulped and washed three times with 300 mL of methanol, and vacuum dried at 80°C for 8 hours to obtain 285.0 g of polyphenylene ether (XSPPO), Mn=1750, Mw=2030.

[0159] 120 mL of toluene, 60 g of polyphenylene ether (SXPPO), 60 mL of 50% sodium hydroxide solution, 4 g (0.043 mol) of tetrabutyl bromide ammonium, 0.1 g of 701 polymerization inhibitor, and 15 g (0.18 mol) of p-chloromethylstyrene were added to a 500 mL four-necked bottle; the temperature was raised to 70 °C under nitrogen protection while stirring, and the reaction was carried out by stirring for 8 hours; the mixture was cooled to room temperature, neutralized to neutral with 10% dilute hydrochloric acid, the organic phase was washed three times with 200 mL of water, added to 800 mL of methanol, the precipitated precipitate was filtered, washed with methanol / water (weight ratio 80:20), vacuum dried at 80 °C for 8 hours, and 82 g of modified polyphenylene ether (XSmPPO) It was obtained, Mn=1860, Mw=2180, and the structural formula of XSmPPO is as follows.

[0160]

[0161] 4 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF) prepared in Example 1, 16 g of XSmPPO, and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene, and after removing the solvent by reduced pressure, a crosslinked resin was prepared by melt injection (thermal curing conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min). The glass transition temperature was measured, and the crosslinked resin was prepared into 80 mm x 80 mm x 0.4 mm thin sections. The dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0162] Example 12

[0163] 9,9-bis(4-vinylbenzyl)-9H-fluorene (p, p-BVBF) was prepared according to the method of Example 9, and

[0164] A modified polyphenylene ether (XSmPPO) was prepared according to the method of Example 11, and

[0165] 4 g (0.01 mol) of p, p-BVBF, 16 g of XSmPPO, and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene, and after removing the solvent by reduced pressure, a crosslinked polymer was prepared by melt injection (thermal curing conditions: temperature 220°C, pressure 70–80 mmHg, time 100 min), the glass transition temperature was measured, and the crosslinked polymer was prepared into 80 mm x 80 mm x 0.4 mm thin sections, and the dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0166] Example 13

[0167] 9,9-bis(4-vinylbenzyl)-9H-fluorene (p, p-BVBF) was prepared according to the method of Example 9, and

[0168] A modified polyphenylene ether (XSmPPO) was prepared according to the method of Example 11, and

[0169] 2 g (0.005 mol) of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o, p-BVBF) prepared in Example 1, 2 g (0.005 mol) of p, p-BVBF, 16 g of XSmPPO, and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene, and after removing the solvent by reduced pressure, a crosslinked polymer was prepared by melt injection (thermal curing conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), the glass transition temperature was measured, and the crosslinked polymer was prepared into 80 mm x 80 mm x 0.4 mm thin sections, and the dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0170] Comparative Example 1

[0171] 20 g of 1,2-bis(4-vinylphenyl)ethane (BVPE) and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene, and after removing the solvent by reduced pressure, a thermosetting hydrocarbon resin was prepared by melt injection (thermal curing conditions: temperature 220°C, pressure 70–80 mmHg, time 100 min), the glass transition temperature was measured, and resin flakes of 80 mm x 80 mm x 0.4 mm were prepared, and the dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0172] Comparative Example 2

[0173] Modified polyphenylene ether (XSmPPO) was prepared according to the method of Example 11, and

[0174] 20 g of modified polyphenylene ether (XSmPPO) and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene, and after removing the solvent by reduced pressure, a thermosetting resin was prepared by melt injection (thermal curing conditions: temperature 220°C, pressure 70–80 mmHg, time 100 min), the glass transition temperature was measured, and the resin was prepared into 80 mm x 80 mm x 0.4 mm thin sections. Then, the dielectric constant and dielectric loss tangent at a frequency of 10 GHz of the sample were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0175] Comparative Example 3

[0176] Modified polyphenylene ether (XSmPPO) was prepared according to the method of Example 11, and

[0177] 2.34 g (0.01 mol) of 1,2-bis(4-vinylphenyl)ethane (BVPE), 17.66 g of modified polyphenylene ether (XSmPPO), and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene, and after removing the solvent under reduced pressure, a crosslinked matrix was prepared by melt injection (thermal curing conditions: temperature 220°C, pressure 70–80 mmHg, time 100 min), the glass transition temperature was measured, and the crosslinked matrix was prepared into 80 mm x 80 mm x 0.4 mm thin strips, and the dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured using an Angelent N5230A vector network analyzer, and the results are listed in Table 4.

[0178] Performance parameters of the thermosetting resins prepared in Examples 8–13 and Comparative Examples 1–3 Examples Substance dosage (g) performance o,p-BVBF p,p-BVBF BVPE XSmPPO Initiator Dk (10 GH) Df (10 GH) Tg(℃) Example 8 20 0 0 0 0.1 2.8 0.00030 360 Example 9 0 20 0 0 0.1 2.8 0.00047 320 Example 10 10 10 0 0 0.1 2.8 0.00042 352 Example 11 4g (0.01mol) 0 0 16 0.1 2.8 0.00060 285 Example 12 0 4g (0.01mol) 0 16 0.1 2.8 0.00070 256 Example 13 2g (0.005mol) 2g (0.005mol) 0 16 0.1 2.8 0.00065 261 Comparative Example 1 0 0 20 0 0.1 2.8 0.00080 312 Comparative Example 2 0 0 0 20 0.1 3.2 0.00250 222 Comparative Example 3 0 0 2.34g (0.01mol) 17.66 0.1 3.2 0.00120 230

[0179] In Table 4, Dk is the dielectric constant, Df is the dielectric loss tangent, and Tg is the glass transition temperature.

[0180] As can be seen from Table 4, thermosetting hydrocarbon resins prepared using 9,9-bis(4-vinylbenzyl)-9H-fluorene have very low dielectric loss tangents and significantly high glass transition temperatures (Examples 8, 9, and 10). Among them, the thermosetting hydrocarbon resin prepared using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o, p-BVBF) has the lowest dielectric loss tangent and the highest glass transition temperature (Example 8). In the case of a crosslinked resin composed of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o, p-BVBF) (Example 11), 9, 9-bis(4-vinylbenzyl)-9H-fluorene (p, p-BVBF) (Example 12), or a 1:1 mixture of the two (Example 13) and terminal vinyl-modified polyphenylene ether, compared to a crosslinked resin of the commonly used crosslinking agent 1, 2-bis(4-vinylphenyl)ethane (BVPE) and terminal vinyl-modified polyphenylene ether (Comparative Example 3), the dielectric constant is significantly lower, the dielectric loss tangent is significantly lower, and the glass transition temperature is much higher. Furthermore, as the weight ratio of o, p-BVBF used as the crosslinking agent increases, the dielectric loss tangent becomes even lower and the glass transition temperature becomes even higher. Therefore, the thermosetting crosslinked resin using the thermosetting hydrocarbon resin and modified polyphenylene ether of the present invention has excellent overall physical properties and can be utilized as a resin material for high-frequency, high-speed printed circuit boards.

[0181] Although the present invention has been specifically described in the above embodiments, this is merely a part of the embodiments of the present invention and does not describe all embodiments. People can obtain other embodiments based on these embodiments without exercising creativity, and all such embodiments fall within the scope of protection of the present invention.

Claims

Claim 1 In the case of asymmetric divinylbenzyl fluorene, it is 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene having a structure represented by Formula 1, and Asymmetric divinylbenzyl fluorene characterized by the above 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene having a thermal analysis melting endothermic peak of 169–175°C, having a monoclinic system, and a space group of P21 / c. Claim 2 A method for preparing asymmetric divinylbenzyl fluorene according to claim 1, comprising the steps of: mixing fluorene, a basic reagent, a polymerization inhibitor, and a polar aprotic solvent to obtain a mixed system containing fluorene; and sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the mixed system containing fluorene, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the mixed system containing fluorene to carry out a nucleophilic substitution reaction to obtain the asymmetric divinylbenzyl fluorene. Claim 3 In paragraph 2, the basic reagent comprises one or more of alkali metal hydroxide, alkali metal alkoxide, sodium hydride, and potassium hydride, the polymerization inhibitor 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-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide, the polar aprotic solvent comprises dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, or hexamethylphosphoramide, and the molar ratio of the fluorene to the basic reagent is A method for preparing asymmetric divinylbenzyl fluorene, characterized in that the ratio is 1:1.8~5, the molar ratio of 2-vinylbenzyl chloride to 4-vinylbenzyl chloride is 2~6:4~8, and the molar ratio of the total moles of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to fluorene is 1.8~2.2:

1. Claim 4 A method for producing asymmetric divinylbenzyl fluorene according to claim 3, characterized in that the temperature of the nucleophilic substitution reaction is 20 to 50°C and the time is 2 to 8 hours. Claim 5 A method for producing asymmetric divinylbenzyl fluorene according to claim 1, comprising the steps of: mixing fluorene, a basic reagent, a polymerization inhibitor, a phase transition catalyst, and a solvent to obtain a phase transition catalyst system containing fluorene; and sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing phase transition catalyst system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing phase transition catalyst system, and carrying out a nucleophilic substitution reaction under phase transition catalyst conditions to obtain the asymmetric divinylbenzyl fluorene. Claim 6 In claim 5, the basic reagent comprises an alkali metal hydroxide and / or an alkali metal alkoxide, the polymerization inhibitor 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-butyl-catechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide, the phase transition catalyst comprises one or more of a quaternary ammonium salt, a quaternary phosphonium salt, and polyethylene glycol, the mass of the phase transition catalyst is 5 to 25% of the mass of fluorene, and the molar ratio of fluorene to the basic reagent is 1:

1. A method for preparing asymmetric divinylbenzyl fluorene, characterized in that the molar ratio of 2-vinylbenzyl chloride to 4-vinylbenzyl chloride is 8 to 5, the molar ratio of 2-vinylbenzyl chloride to 4-vinylbenzyl chloride is 2 to 6:4 to 8, and the molar ratio of the total molar amount of 2-vinylbenzyl chloride to 4-vinylbenzyl chloride to fluorene is 1.8 to 2.2:

1. Claim 7 A method for producing asymmetric divinylbenzyl fluorene according to claim 6, characterized in that the temperature of the nucleophilic substitution reaction under the above-mentioned phase transition catalyst conditions is 25 to 75°C and the time is 8 to 18 hours. Claim 8 The thermosetting hydrocarbon resin and / or thermosetting crosslinking resin comprises, wherein the thermosetting hydrocarbon resin comprises a thermosetting hydrocarbon resin manufactured using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene as a raw material and / or a thermosetting hydrocarbon resin manufactured using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and 9,9'-bis(4-vinylbenzyl)-9H-fluorene as raw materials, and the thermosetting crosslinking resin comprises a thermosetting crosslinking resin obtained using a crosslinking agent and terminal alkenyl polyphenylene ether as raw materials, and the crosslinking agent comprises 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and / or 9, It comprises 9'-bis(4-vinylbenzyl)-9H-fluorene, wherein the terminal alkenyl polyphenylene ether has a structure shown in any one of Formulas 2 to 5, Equation 2 Equation 3 Equation 4 A thermosetting resin characterized in that the above 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene is the asymmetric divinylbenzyl fluorene described in claim 1, or the asymmetric divinylbenzyl fluorene produced by the manufacturing method described in any one of claims 2 to 7. Claim 9 A method for manufacturing a thermosetting resin according to claim 8, characterized by comprising the steps of: dissolving a manufacturing raw material and an initiator in toluene to obtain a mixed solution; and removing the toluene from the mixed solution and then melting and thermosetting to obtain the thermosetting resin.

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