Asymmetrical bisvinylbenzylfluorene, thermosetting hydrocarbon resin, thermosetting crosslinked resin, and methods for preparing and using the same.

Abstract

This invention provides high-frequency, high-speed substrate materials, as well as methods for preparing and using them. [Solution] The present invention provides asymmetric bisvinylbenzylfluorene (9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene, o,p-BVBF) and its thermosetting hydrocarbon resin, as well as a thermosetting hydrocarbon resin of o,p-BVBF and symmetric bisvinylbenzylfluorene (9,9'-bis(4-vinylbenzyl)-9H-fluorene, p,p-BVBF), and a thermosetting crosslinked resin obtained by crosslinking o,p-BVBF and / or p,p-BVBF with terminal alkenyl polyphenylene ethers as a crosslinking agent, and a method for preparing and using the same. All of these resins have very low dielectric constants and dielectric loss tangents, and very high glass transition temperatures, and have very good application prospects as resins for high-frequency, high-speed substrates.

Description

Technical Field

[0001] The present invention belongs to the technical field of high-frequency high-speed substrate materials, and specifically relates to asymmetric bisvinylbenzyl fluorene, thermosetting hydrocarbon resins, thermosetting crosslinked modified polyphenylene ether resins, and preparation methods and uses thereof.

Background Art

[0002] With the rapid development of 5G / 6G communication, artificial intelligence, AR / VR, satellite navigation and autonomous driving, electronic products require high frequency, high speed and larger capacity for transmitting voice, video and data. At the same time, electronic products tend to be lighter, thinner and smaller. In order to maintain higher transmission speed and signal integrity, the laminated resin material of printed circuit board (PCB), which is the core component of electronic products, needs to have lower dielectric constant, lower dielectric loss tangent, higher glass transition temperature, and higher peel strength. Therefore, further improving the dielectric properties and thermomechanical properties of resin materials has become an important technical issue to be solved at present.

[0003] Epoxy resin is a main resin material used for printed circuit boards due to its low cost, but it has a relatively high dielectric constant and a high dielectric loss tangent, so it is difficult to achieve an appropriate low dielectric loss tangent under high-frequency signals, and it is difficult to meet the requirements of high-speed signal transmission. Fluororesin represented by polytetrafluoroethylene has the properties of low dielectric constant and low dielectric loss tangent, but since it is a thermoplastic resin, it is difficult to process and mold for producing multilayered, lightweight, thin, and miniaturized printed circuit boards. Modified polyphenylene ether (mPPO) capped with low molecular weight vinylbenzyl or acryloyl has low dielectric constant and dielectric loss tangent, and the polyphenylene ether crosslinked resin crosslinked with mPPO and bisolefin (e.g., 1,2-bis(4-vinylphenyl)ethane, BVPE) has high thermomechanical properties and is used as a laminate resin material for high-end printed circuit boards (PCBs).

[0004] 9,9-disubstituted fluorenyl hydrocarbon derivatives, due to their unique Cardo structure, 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, and are widely used as materials for microelectronic devices.

[0005] Patent Document 1 discloses a mixture prepared by reacting vinylbenzyl chloride (a mixture of meta-isomers and para-isomers in a mass ratio of 1:1) and allyl chloride with fluorene. The thermosetting resin has a dielectric constant (5 GHz) of 4.0 and a dielectric loss tangent (5 GHz) of 0.0035, which are clearly too high. Furthermore, because of the presence of allyl groups on the 9-fluorenyl groups, the glass transition temperature of the mixture is low. Patent Document 2 discloses a thermosetting resin made from a mixture of vinylbenzylindene and 9,9-bisvinylbenzyl-9H-fluorene containing meta-isomers, with a dielectric loss tangent (10 GHz) of 0.00089. For a resin used in high-frequency, high-speed substrates, its dielectric constant and dielectric loss tangent are still too high. In addition, Patent Document 2 uses bismaleimide as a crosslinking agent to increase the glass transition temperature. Since bismaleimide contains polar groups, it can increase the glass transition temperature, but this results in a high dielectric loss tangent. Patent Document 3 discloses that a mixture of fluorene is prepared by reacting a mixture of vinylbenzyl chloride (meth-isomers and para-isomers in a mass ratio of 1:1) with fluorene to obtain a mixture of meta-isomers and para-isomers of 9,9-bis(vinylbenzyl)-9H-fluorene, which has a melting point of 142°C. The dielectric constant and dielectric loss tangent (1 MHz) of this thermosetting resin are 0.0013, and its dielectric loss tangent is clearly high, making it unsuitable as a resin material for high-frequency, high-speed substrates.

[0006] To meet the high-frequency, high-speed transmission needs of next-generation printed circuit board laminates, further reducing the dielectric constant and dielectric loss tangent of the resin material of the printed circuit board and further increasing the glass transition temperature are important technological challenges that need to be addressed today. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2003-283076 [Patent Document 2] International Publication No. 2022 / 207741 [Patent Document 3] Chinese Patent Application Publication No. 1501899 Specification [Overview of the project] [Problems that the invention aims to solve]

[0008] In view of this, the present invention provides asymmetric bisvinylbenzylfluorene, a thermosetting hydrocarbon resin using asymmetric bisvinylbenzylfluorene as a raw material, a method for preparing the same and its use, a thermosetting hydrocarbon resin using asymmetric bisvinylbenzylfluorene and / or symmetric bisvinylbenzylfluorene as a raw material, a method for preparing the same and its use, and further provides a thermosetting crosslinked polyphenylene ether resin in which asymmetric bisvinylbenzylfluorene, symmetric bisvinylbenzylfluorene, or a mixture thereof is crosslinked with a terminal alkenyl polyphenylene ether as a crosslinking agent, a method for preparing the same and its use. The asymmetric bisvinylbenzylfluorene (9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene, o,p-BVBF) provided by the present invention is a nonpolar total hydrocarbon compound, and at the same time, the two asymmetric substituents of the fluorenyl group at position 9 constitute a rigid cardo structure. Therefore, thermosetting hydrocarbon resins and thermosetting crosslinked polyphenylene ether resins have a small dielectric loss tangent, a low dielectric constant, and a high glass transition temperature, giving them good prospects for application as resin materials for high-frequency, high-speed substrates. [Means for solving the problem]

[0009] To solve the above technical problems, the present invention provides an asymmetric bisvinylbenzylfluorene, which is 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene having the structure shown in Formula 1, [ka] Thermal analysis of the aforementioned 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene revealed a melting endothermic peak at 169-175°C, indicating a monoclinic crystal system and a space group of P21 / c.

[0010] The present invention further provides a method for preparing asymmetric bisvinylbenzylfluorene as described in the above technical solution, The steps include: mixing fluorene, an alkaline reagent, a polymerization inhibitor, and a polar aprotic solvent to obtain a fluorene-containing mixture; The method includes the steps of sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing mixed system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing mixed system to carry out a nucleophilic substitution reaction to obtain the asymmetric bisvinylbenzylfluorene.

[0011] Preferably, the alkaline reagent comprises one or more of alkali metal hydroxides, alkali metal alkoxides, sodium hydride, and potassium hydride. The polymerization inhibitor comprises one or more of the following: nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide. The polar aprotic solvent includes dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, or hexamethylphosphoramide. The molar ratio of fluorene to alkaline reagent is 1:1.8 to 5. The molar ratio of 2-vinylbenzyl chloride to 4-vinylbenzyl chloride is 2-6:4-8. The molar ratio of the total molar amounts of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to fluorene is 1.8 to 2.2:1.

[0012] Preferably, the temperature of the nucleophilic substitution reaction is 20 to 50°C, and the duration is 2 to 8 hours.

[0013] The present invention further provides a method for preparing asymmetric bisvinylbenzylfluorene as described in the above technical solution, The steps include: mixing fluorene, an alkaline reagent, a polymerization inhibitor, a phase transfer catalyst, and a solvent to obtain a fluorene-containing phase transfer catalyst system; The method includes the steps of sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing phase-transfer catalyst system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing phase-transfer catalyst system, carrying out a nucleophilic substitution reaction under phase-transfer catalytic conditions, and obtaining the asymmetric bisvinylbenzylfluorene.

[0014] Preferably, the alkaline reagent comprises an alkali metal hydroxide and / or alkali metal alkoxide. The polymerization inhibitor comprises one or more of the following: nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide. The phase transfer catalyst comprises one or more of the following: a quaternary ammonium salt, a quaternary phosphonium salt, and polyethylene glycol. The mass of the phase transfer catalyst is 5-25% of the mass of fluorene. The molar ratio of fluorene to alkaline reagent is 1:1.8 to 5. The molar ratio of 2-vinylbenzyl chloride to 4-vinylbenzyl chloride is 2-6:4-8. The molar ratio of the total molar amount of the 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to fluorene is 1.8~2.2:1.

[0015] Preferably, the temperature of the nucleophilic substitution reaction under said phase transfer catalysis conditions is 25~75°C, and the reaction time is 8~18h.

[0016] The present invention further 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 prepared using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene as a preparation raw material and / or a thermosetting hydrocarbon resin prepared using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene and 9,9'-bis(4-vinylbenzyl)-9H-fluorene as preparation raw materials, the thermosetting crosslinked resin comprises a thermosetting crosslinked resin prepared using a crosslinking agent and a terminal alkenyl polyphenylene ether as preparation raw materials, 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 represented by any one of formulas 2 to 5,

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

[0017] The present invention further provides a method for preparing a thermosetting resin as described in the above technical solution, The steps include: dissolving the raw materials and initiator in toluene to obtain a mixed solution; The process includes the step of removing toluene from the mixed solution, then performing melt-heat curing to obtain the thermosetting resin.

[0018] The present invention further provides the use of the thermosetting resin described in the above technical solution or a thermosetting resin prepared by the preparation method described in the above technical solution as a resin material for high-frequency, high-speed substrates. [Effects of the Invention]

[0019] The present invention provides an asymmetric bisvinylbenzylfluorene having the structure shown in Formula 1, wherein the fusion endothermic peak of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene, as determined by thermal analysis, is 169-175°C, has a monoclinic crystal system, and its space group is P21 / c. The bisvinylbenzylfluorene (9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) provided by the present invention has an asymmetric structure and is a nonpolar total hydrocarbon compound. At the same time, the two asymmetric substituents of the fluorenyl group at position 9 constitute a rigid cordo structure. Therefore, thermosetting resins prepared using the asymmetric bisvinylbenzylfluorene provided by the present invention as a raw material have the characteristics of a small dielectric loss tangent, a low dielectric constant, a high glass transition temperature, and ease of processing, and can be used as resin materials for high-frequency, high-speed substrates. [Brief explanation of the drawing]

[0020] [Figure 1] This is a schematic diagram of the synthesis process of asymmetric bisvinylbenzylfluorene via nucleophilic substitution. [Figure 2] This is the HPLC spectrum of o,p-BVBF prepared in Example 1. [Figure 3] This is the 1H NMR spectrum of o,p-BVBF prepared in Example 1. [Figure 4]This is the 13C NMR spectrum of o,p-BVBF prepared in Example 1. [Figure 5] This is the thermal analysis DSC spectrum of o,p-BVBF prepared in Example 1. [Figure 6] This is a single crystal structure diagram of o,p-BVBF prepared in Example 1. [Figure 7] This is a unit cell packing diagram of the o,p-BVBF prepared in Example 1. [Modes for carrying out the invention]

[0021] The present invention synthesizes an asymmetric bisvinylbenzylfluorene, which is 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) having the structure shown in Formula 1. [ka] Thermal analysis of the aforementioned 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene revealed a melting endothermic peak at 169-175°C, indicating a monoclinic crystal system and a space group of P21 / c.

[0022] In the present invention, the term "asymmetric" in "asymmetric bisvinylbenzylfluorene" means that a different substituent exists at the 9-position of the fluorenyl group.

[0023] In a specific embodiment of the present invention, the endothermic melting peak of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene obtained by thermal analysis is 169-175°C, but may be 171-173°C, and the purity (HPLC) of the asymmetric bisvinylbenzylfluorene may be greater than 98.5%.

[0024] The present invention synthesizes 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) using two methods.

[0025] The present invention further provides a first method for preparing asymmetric bisvinylbenzylfluorene as described in the above technical solution, The steps include: mixing fluorene, an alkaline reagent, a polymerization inhibitor, and a polar aprotic solvent to obtain a fluorene-containing mixture; The method includes the steps of sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing mixed system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing mixed system to carry out a nucleophilic substitution reaction to obtain the asymmetric bisvinylbenzylfluorene.

[0026] In specific embodiments of the present invention, the alkaline reagent may contain one or more of alkali metal hydroxides, alkali metal alkoxides, sodium hydride, and potassium hydride. Specifically, it may be a mixture of alkali metal hydroxide and alkali metal alkoxide, alkali metal hydroxide, alkali metal alkoxide, sodium hydride, or potassium hydride. The alkali metal hydroxide may be sodium hydroxide or potassium hydroxide. The alkali metal alkoxide may be potassium tert-butoxide or sodium tert-butoxide. The molar ratio of fluorene to the alkaline reagent may be 1:1.8 to 5 or 1:2 to 4.

[0027] In specific embodiments of the present invention, the polymerization inhibitor may include one or more of the following: nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide (701 polymerization inhibitor). Specifically, nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide (701 polymerization inhibitor). The polymerization inhibitor may be trophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, or a 701 polymerization inhibitor. The amount of the polymerization inhibitor used may be 0.01 to 0.5% or 0.1 to 0.4% of the mass of vinylbenzyl chloride, and the vinylbenzyl chloride may be 2-vinylbenzyl chloride or 4-vinylbenzyl chloride.

[0028] In specific embodiments of the present invention, the polar aprotic solvent includes dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, or hexamethylphosphoramide, and in the present invention, the amount of the polar aprotic solvent used is not particularly limited as long as the materials can be uniformly mixed.

[0029] In the present invention, there are no special requirements for the mixing of the fluorene, alkaline reagent, polymerization inhibitor, and polar aprotic solvent, as long as they can be mixed uniformly.

[0030] In the present invention, first adding 2-vinylbenzyl chloride dropwise to the fluorene-containing mixed system to produce a monosubstituted 9-(2-vinylbenzyl)fluorene intermediate, and then adding 4-vinylbenzyl chloride dropwise to react, significantly improves the yield of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) compared to directly adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise. First, 4-vinylbenzyl chloride is added dropwise, and then 2-vinylbenzyl chloride is added and the reaction proceeds. This mainly yields 9,9'-bis-(4-vinylbenzyl)fluorene (p,p-BVBF), 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 it is difficult to introduce the 2-vinylbenzyl group when a 4-vinylbenzyl group is already present at the fluorenyl group at position 9.

[0031] In a specific embodiment of the present invention, the molar ratio of 2-vinylbenzyl chloride to 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 molar amounts of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to fluorene may be 1.8 to 2.2:1, specifically 2:1.

[0032] In a specific embodiment of the present invention, the temperature of the nucleophilic substitution reaction may be 20 to 50°C or 30 to 40°C, and the duration of the nucleophilic substitution reaction 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 carried out under stirring conditions. In the present invention, the stirring is not particularly limited.

[0033] As a specific embodiment of the present invention, after the nucleophilic substitution reaction, The steps include mixing the system after the nucleophilic substitution reaction with ice water, then separating the solid and liquid to obtain a solid, The process may further include the steps of washing the solid with water, then sequentially beating, filtering, recrystallizing, and drying to obtain the asymmetric bisvinylbenzylfluorene.

[0034] In a specific embodiment of the present invention, the volume ratio of the system after the nucleophilic substitution reaction to ice water may be 3:8 to 12 or 3:10 to 11, the solid-liquid separation may be by filtration, and in the present invention, there are no special requirements for the number of water washes as long as the pH value of the filtrate after water washing is neutral. In a specific embodiment of the present invention, the solvent for beating may be an alcohol-based solvent, and the alcohol-based solvent may include methanol, ethanol, or isopropanol, and the beating temperature may be 0 to 40°C or 10 to 30°C. In the present invention, the filtration is not particularly limited and any conventional method in the art may be used. In a specific embodiment of the present invention, the solvent for recrystallization may include toluene, ethylbenzene, xylene, or cumene, the drying may be vacuum drying, the vacuum drying temperature may be 70 to 90°C or 75 to 80°C, and in the present invention, there are no special requirements for the vacuum drying time as long as the solvent can be removed.

[0035] The present invention further provides a second method for preparing asymmetric bisvinylbenzylfluorene as described in the above technical solution, The steps include: mixing fluorene, an alkaline reagent, a polymerization inhibitor, a phase transfer catalyst, and a solvent to obtain a fluorene-containing phase transfer catalyst system; The method includes the steps of sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing phase-transfer catalyst system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing phase-transfer catalyst system, carrying out a nucleophilic substitution reaction under phase-transfer catalytic conditions, and obtaining the asymmetric bisvinylbenzylfluorene.

[0036] In specific embodiments of the present invention, the alkaline reagent may include alkali metal hydroxides and / or alkali metal alkoxides, specifically a mixture of alkali metal hydroxides and alkali metal alkoxides, alkali metal hydroxides, or alkali metal alkoxides. 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. The molar ratio of fluorene to the alkaline reagent may be 1:1.8 to 5 or 1:2 to 4.

[0037] In specific embodiments of the present invention, the polymerization inhibitor may include one or more of the following: nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide (701 polymerization inhibitor). Specifically, nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide (701 polymerization inhibitor). The polymerization inhibitor may be trophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, or a 701 polymerization inhibitor. The amount of the polymerization inhibitor used may be 0.01 to 0.5% or 0.1 to 0.4% of the mass of vinylbenzyl chloride, and the vinylbenzyl chloride may be 2-vinylbenzyl chloride or 4-vinylbenzyl chloride.

[0038] In a specific embodiment of the present invention, the phase transfer catalyst may contain one or more of quaternary ammonium salts, quaternary phosphonium salts, and polyethylene glycol, and more specifically, it may be a quaternary ammonium salt, a quaternary phosphonium salt, or polyethylene glycol, where the quaternary ammonium salt is tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), benzyltriethylammonium bromide (BTEAB), benzyltriethylammonium chloride (BTEAC), or hexadecyltriethylammonium bromide (HTE). The quaternary phosphonium salt may be AB) or hexadecyltriethylammonium chloride (HTEAC), and the quaternary phosphonium salt may be hexadecyltributylphosphonium bromide (HTBPB), hexadecyltributylphosphonium chloride (HTBPC), tetrabutylphosphonium bromide (TBPB), tetrabutylphosphonium chloride (TBPC), tetraphenylphosphonium bromide (TPPB), or tetraphenylphosphonium chloride (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 transfer catalyst may be 5 to 25% or 10 to 20% of the mass of fluorene.

[0039] As a specific embodiment of the present invention, the nucleophilic substitution reaction under the phase-transfer catalyst conditions may be a nucleophilic substitution reaction under liquid-liquid phase-transfer catalyst conditions or a nucleophilic substitution reaction under solid-liquid phase-transfer catalyst conditions.

[0040] In a specific embodiment of the present invention, when the nucleophilic substitution reaction under phase-transfer catalytic conditions is a reaction under solid-liquid phase-transfer catalytic 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.

[0041] In a specific embodiment of the present invention, when the nucleophilic substitution reaction under phase-transfer catalytic conditions is a reaction under liquid-liquid phase-transfer catalytic conditions, the solvent may be a mixture of aromatic hydrocarbons and water or a mixture of alkanes and water, the aromatic hydrocarbon may be toluene, xylene, ethylbenzene, or cumene, and the alkane may be n-hexane, n-heptane, cyclohexane, methylcyclopentane, or petroleum ether.

[0042] In the present invention, first adding 2-vinylbenzyl chloride dropwise to produce a monosubstituted 9-(2-vinylbenzyl)fluorene intermediate, and then adding 4-vinylbenzyl chloride dropwise to react, significantly improves the yield of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) compared to directly adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise. When 4-vinylbenzyl chloride is added dropwise first, followed by 2-vinylbenzyl chloride, the reaction mainly yields 9,9'-bis-(4-vinylbenzyl)fluorene (p,p-BVBF), 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 it is difficult to introduce the 2-vinylbenzyl group when a 4-vinylbenzyl group is already present at the fluorenyl group at position 9. Therefore, adding 2-vinylbenzyl chloride dropwise first, allowing it to react for a certain period of time, and then adding 4-vinylbenzyl chloride dropwise is advantageous in improving the yield of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF).

[0043] In a specific embodiment of the present invention, the molar ratio of 2-vinylbenzyl chloride to 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 molar amounts of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to fluorene may be 1.8 to 2.2:1, specifically 2:1.

[0044] In a specific embodiment of the present invention, the temperature of the nucleophilic substitution reaction under the phase-transfer catalyst conditions may be 25 to 75°C or 30 to 70°C, and the duration of the nucleophilic substitution reaction under the phase-transfer 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-transfer catalyst conditions must be carried out under good stirring conditions.

[0045] As a specific embodiment of the present invention, after the nucleophilic substitution reaction under the phase transfer catalyst conditions, The system after the nucleophilic substitution reaction under the aforementioned phase-transfer catalyst conditions is distilled to remove the solvent, and then water and toluene are added for extraction to extract the organic phase. The method may further include the steps of concentrating the organic phase, then sequentially washing, beating, filtering, recrystallizing, and drying to obtain the asymmetric bisvinylbenzylfluorene.

[0046] In a specific embodiment of the present invention, the volume ratio of water to toluene for extraction may be 1:0.8 to 1.2 or 1:1, and the concentration may be by vacuum distillation. In the present invention, there are no special requirements for vacuum distillation as long as the solvent can be removed. In a specific embodiment of the present invention, the solvent for washing may be a saturated ammonium chloride solution. In the present invention, there are no special requirements 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 for beating may be an alcohol-based solvent having 5 or fewer carbon atoms, and the alcohol-based solvent having 5 or fewer carbon atoms may include methanol, ethanol, or isopropanol. The beating temperature may be 0 to 40°C or 10 to 30°C. In the present invention, the filtration is not particularly limited, and any conventional method in the art may be used. In specific embodiments of the present invention, the solvent for recrystallization may include toluene, ethylbenzene, xylene, or cumene, the drying may be vacuum drying, the temperature of the vacuum drying may be 70-90°C or 75-80°C, and in the present invention, there are no special requirements for the time of the vacuum drying as long as the solvent can be removed.

[0047] Figure 1 is a schematic diagram of the synthesis process of asymmetric bisvinylbenzylfluorene by nucleophilic substitution reaction.

[0048] The present invention further 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 prepared using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene as a raw material and / or 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. The thermosetting crosslinked resin comprises a thermosetting crosslinked resin prepared 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 represented by any one of formulas 2 to 5. [ka] [ka] [ka] [ka] The 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene is the asymmetric bisvinylbenzylfluorene described in the above technical solution or the asymmetric bisvinylbenzylfluorene prepared by the preparation method described in the above technical solution.

[0049] As a specific embodiment of the present invention, a thermosetting hydrocarbon resin prepared 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 (Tg360℃).

[0050] As a specific embodiment of the present invention, the molar percentage of o,p-BVF in 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVF) and 9,9'-bis(4-vinylbenzyl)-9H-fluorene (p,p-BVBF) in the raw materials for a thermosetting hydrocarbon resin prepared using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) may be 10 to 60% or 25 to 50%. In the present invention, the 9,9'-bis(4-vinylbenzyl)-9H-fluorene is a symmetric bisvinylbenzylfluorene, where symmetry means that the same substituent is located at the 9-position of the fluorenyl group, and the structural formula of the 9,9'-bis(4-vinylbenzyl)-9H-fluorene is as follows. [ka]

[0051] 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 fairly high glass transition temperature. For example, when the molar ratio of o,p-BVF to 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°C.

[0052] In a specific embodiment of the present invention, the number average molecular weight (Mn) of the terminal alkenyl polyphenylene ether in a 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 vinyl benzyl modified polyphenylene ether, and the structural formula of the terminal vinyl benzyl modified polyphenylene ether is as follows. [ka]

[0053] As a specific embodiment of the present invention, the method for preparing the terminal vinylbenzyl group-modified polyphenylene ether is as follows: The steps include: obtaining a hydroxypolyphenylene ether by oxidative coupling copolymerization of 2,6-dimethylphenol, a divalent phenol, and a catalyst under oxygen conditions; The process may also include the step of reacting the hydroxypolyphenylene ether with vinyl benzyl chloride under phase-transfer conditions, followed by precipitation with methanol to obtain the terminal vinylbenzyl-modified polyphenylene ether.

[0054] In 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, cuprous bromide, cuprous chloride, cupric chloride, or cupric bromide, and the number average molecular weight of the hydroxypolyphenylene ether may be 1600 to 2000.

[0055] In a specific embodiment of the present invention, when preparing a thermosetting crosslinked resin 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 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) in the crosslinking agent may be 10-60% or 25-50%.

[0056] The thermosetting resin provided by the present invention has a low dielectric constant, a low dielectric loss tangent, and an improved glass transition temperature, and has good potential for application as a resin material for high-frequency substrates.

[0057] The present invention further provides a method for preparing a thermosetting resin as described in the above technical solution, The steps include: dissolving the raw materials and initiator in toluene to obtain a mixed solution; The process includes the step of removing toluene from the mixed solution, then performing melt-heat curing to obtain the thermosetting resin.

[0058] In specific embodiments of the present invention, the initiator may contain a peroxide, which may be di-t-butyl peroxide, t-butyl hydroperoxide, cumene peroxide, t-butyl benzoyl peroxide, di(t-butyl peroxy)isopropylbenzene, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, dilauroyl peroxide, 1,1-di(t-butyl peroxy)cyclohexane, 1,1-di(t-butyl peroxy) The preparation may also contain xy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 3,3,5,7,7-pentamethyl-1,2,4-trioxane (T311), t-butylperoxy-2-ethylhexanoate, and t-butylperoxy-2-hexylhexane carbonate. The mass ratio of the preparation raw materials to the initiator may be 1:0.001 to 0.008 or 1:0.003 to 0.005.

[0059] As a specific embodiment of the present invention, the method for removing toluene from the mixed solution may be vacuum distillation.

[0060] In a specific embodiment of the present invention, the melting and curing temperature may be 200 to 240°C or 210 to 230°C, the melting and curing pressure may be 70 to 80 mmHg or 75 to 78 mmHg, and the melting and curing time may be 80 to 120 min or 90 to 110 min.

[0061] The present invention further provides the use of the thermosetting resin described in the above technical solution or a thermosetting resin prepared by the preparation method described in the above technical solution as a resin material for high-frequency, high-speed substrates.

[0062] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to examples, but these should not be construed as limiting the scope of protection of the present invention.

[0063] The analytical instruments and analytical test methods used in the examples are as follows.

[0064] 1. Purity measurement method (HPLC): Agillent 1260 high-pressure liquid chromatograph (USA); Column type: Kromasil 100-5 C18 250cm × 4.6mm; 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.

[0065] 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.

[0066] 3. Nuclear Magnetic Resonance Spectrum Measurement: Bruker AV 400 nuclear magnetic resonance spectrometer, DMSO-d6 as the solvent, and TMS as the internal standard.

[0067] 4. Measurement of single crystal structure: Bruker D8 Venture single crystal diffractometer, JY / T0588-2020 General Rules for Molecular Structure Analysis.

[0068] 5. Dielectric constant Dk (10 GHz) and dielectric loss tangent Df (10 GHz) measurement: Using the molten sample casting method (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), resin sheets of 80 mm × 80 mm × 0.4 mm were prepared and measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer (SPDR).

[0069] 6. Measurement of polymer molecular weight: US Agillent 1260 gel chromatograph, tetrahydrofuran as mobile phase, polystyrene as standard.

[0070] 7. Measurement of the glass transition temperature of the polymer: Measured using a Perkin Elemer differential scanning calorimeter dsc 4000.

[0071] The 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%) used in the examples were all manufactured by Shandong Xingshun New Materials Co., Ltd.

[0072] Examples 1 to 7 prepare 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF), while Examples 8 to 13 prepare thermosetting resins.

[0073] Example 1 Add 300 mL of anhydrous dimethyl sulfoxide, 1.10 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor to a reaction flask, stir for 30 min under a nitrogen stream, then add 0.5 mol of fluorene, stir to dissolve, then add 0.4 mol of 2-chloromethylstyrene dropwise and react for 1.0 hour under stirring conditions of 30-35°C and 350 r / min, then add 0.6 mol of 4-chloromethylstyrene dropwise under stirring conditions and stir for 2.5 hours. The reaction was continued, and the resulting solution was gradually added to 1000 mL of ice water. The precipitated solid was filtered, washed with water until the filtrate was neutral, and the solid was beaten twice with 500 mL of methanol (30°C). The resulting solid was filtered and recrystallized twice with toluene. The resulting solid was vacuum-dried at 80°C until a constant weight was obtained to yield 144.5 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) with a yield of 72.5%.

[0074] o,p-BVBF is a white crystalline substance. As shown in Figure 2, high-performance liquid chromatography (HPL) chromatography was performed on the prepared o,p-BVBF to obtain the HPL spectrum. Table 1 shows the peak information from the HPL chromatography. From the HPL chromatography detection results, it was found that the HPLC purity of o,p-BVBF was 99.15%.

[0075] As shown in Figures 3-4, nuclear magnetic resonance detection was performed on the prepared o,p-BVBF. 1 1H NMR spectrum and 13 The 13C NMR spectrum was obtained, and Figure 3 shows the spectrum of o,p-BVBF. 1 Figure 4 shows the 1H NMR spectrum of o,p-BVBF. 13 This is a 1C NMR spectrum.

[0076] 1 ¹H NMR (400MHz, DMSO-d6) δ: 3.43 (s, 2H, CH2), 3.54 (s, 2H, CH2), 5.03-5.08 (m, 2H, 2 × olefin-bonded hydrogen), 5.40-5.59 (m, 2H, 2 × olefin-bonded hydrogen), 6.40-6.42 (m, 1H, 1 × olefin-bonded hydrogen), 6.49 (d, 2H, 2 × benzene ring hydrogen), 6.70-6. 77 (m,2H,2×benzene ring hydrogen), 6.97-7.01 (m,3H,2×benzene ring hydrogen,1×olefin bonded hydrogen), 6.87-6.95 (m,1H,1×benzene ring hydrogen), 7.05-7.20 (m,4H,4×fluorene ring hydrogen), 7.22-7.25 (m,1H,1×benzene ring hydrogen), 7.33-7.58 (m,4H,4×fluorene ring hydrogen).

[0077] 13¹³C NMR (100MHz, 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).

[0078] 1 1H NMR spectrum and 13 The 13C NMR spectrum is in perfect agreement with the structure of o,p-BVBF.

[0079] As shown in Figure 5, the prepared o,p-BVBF was detected using a Pyris1 thermal analyzer to obtain a DSC spectrum. From Figure 5, it was found that the melting point of o,p-BVBF is 171.4–172.7°C.

[0080] Figure 6 is a single-crystal structure diagram of o,p-BVBF, where the circles represent H atoms. Figure 7 is a unit cell packing diagram of o,p-BVBF. The crystallographic parameters of o,p-BVBF are shown in Table 2, and the bond length and bond angle data for o,p-BVBF are shown in Table 3. The molecular structure of o,p-BVBF was further confirmed by the results of the single-crystal structure measurement.

[0081] [Table 1]

[0082] [Table 2]

[0083] [Table 3]

[0084] Example 2 Add 300 mL of anhydrous dimethyl sulfoxide, 1.10 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor to a reaction flask. Stir under a nitrogen stream for 30 minutes, then add 0.5 mol of fluorene and stir until dissolved. Add 0.3 mol of 2-chloromethylstyrene dropwise and react for 1.0 hour at 35°C with stirring at 350 r / min. Then, add 0.7 mol of 4-chloromethylstyrene dropwise under stirring conditions and continue reacting with stirring for 2.5 hours. The solution was gradually added to 1000 mL of ice water, the precipitated solid was filtered, washed with water until the filtrate was neutral, the solid was beaten twice with 500 mL of methanol (30°C), filtered, and the resulting solid was recrystallized twice with toluene. The resulting solid was vacuum-dried at 80°C until constant weight was obtained, yielding 110.8 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) as white crystals. The purity (HPLC) was 99.1% and the yield was 55.6%.

[0085] Example 3 Add 300 mL of anhydrous dimethyl sulfoxide, 1.10 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor to a reaction flask. Stir under a nitrogen stream for 30 minutes, then add 0.5 mol of fluorene and stir until dissolved. Add 0.5 mol of 2-chloromethylstyrene dropwise and react for 1.0 hour at 35°C with stirring at 350 r / min. Then, add 0.5 mol of 4-chloromethylstyrene dropwise under stirring conditions and continue reacting with stirring for 2.5 hours. The solution was gradually added to 1000 mL of ice water, the precipitated solid was filtered, washed with water until the filtrate was neutral, the solid was beaten twice with 500 mL of methanol (30°C), filtered, and the resulting solid was recrystallized twice with toluene. The resulting solid was vacuum-dried at 80°C until constant weight was obtained, yielding 126.7 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) as white crystals. The purity (HPLC) was 99.2% and the yield was 63.6%.

[0086] Example 4 Add 300 mL of anhydrous dimethyl sulfoxide, 1.10 mol of potassium tert-butoxide, and 0.3 g of 701 polymerization inhibitor to a reaction flask. Stir under a nitrogen stream for 30 minutes, then add 0.5 mol of fluorene and stir until dissolved. Add a mixed solution of 0.4 mol of 2-chloromethylstyrene and 0.6 mol of 4-chloromethylstyrene dropwise, and react for 3.5 hours at 35°C with stirring at 350 r / min. After the reaction, cool the solution in 1000 ml of ice water. The solid was gradually added to L, filtered, washed with water until the filtrate was neutral, beaten twice with 500 mL of methanol (30°C), filtered, and the resulting solid was recrystallized twice with toluene. The resulting solid was vacuum-dried at 80°C until constant weight was obtained, yielding 90.6 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) as white crystals. The purity (HPLC) was 98.5% and the yield was 45.5%.

[0087] Example 5 Add 500 mL of toluene and 0.5 mol of fluorene to the reaction flask, stir to dissolve, and while stirring, add 180 g of the pre-prepared 50% sodium hydroxide solution, 8.5 g of tetrabutylammonium bromide (TBAB), and 0.3 g of 701 polymerization inhibitor, and while stirring, add 0.4 mol of 2-chloromethylstyrene dropwise at 40°C under a nitrogen stream, and react for 4.0 hours under stirring conditions of 350 r / min, then while stirring, add 0.6 mol of 4-chloromethylstyrene dropwise, continue reacting with stirring for 10 hours, cool to room temperature, and while stirring, gradually add 500 mL of water, The organic phase was separated and washed twice with 500 mL of water each time. The organic phase was then washed with 500 mL of saturated ammonium chloride aqueous solution, followed by washing with water until neutral. The organic phase was separated, toluene was evaporated under reduced pressure, the solid was beaten twice with 500 mL of methanol (30°C), filtered, and the resulting solid was recrystallized twice with toluene. The resulting solid was vacuum-dried at 80°C until constant weight was obtained, yielding 124.3 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) as white crystals. The purity (HPLC) was 98.5% and the yield was 62.4%.

[0088] Example 6 Add 500 mL of toluene and 0.5 mol of fluorene to the reaction flask, stir to dissolve, and while stirring, add 180 g of a pre-prepared 50% sodium hydroxide solution, 8.5 g of tetrabutylammonium bromide (TBAB), and 0.3 g of 701 polymerization inhibitor, and at 40°C, under a nitrogen stream, add a mixed solution of 0.5 mol of 2-chloromethylstyrene and 0.5 mol of 4-chloromethylstyrene dropwise while stirring, and react for 14.0 hours under stirring conditions of 350 r / min, cool to room temperature, and while stirring, gradually add 500 mL of water to separate the organic phase, and each time The organic phase was washed twice with 500 mL of water, washed with 500 mL of saturated ammonium chloride aqueous solution, washed with water until neutral, separated the organic phase, evaporated toluene under reduced pressure, beaten the solid twice with 500 mL of methanol (30°C), filtered the solid, recrystallized twice with toluene, and vacuum-dried the obtained solid at 80°C until constant weight was achieved to obtain 84.7 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) as white crystals. The purity (HPLC) was 98.5% and the yield was 42.5%.

[0089] Example 7 Add 500 mL of acetonitrile, 1.2 mol of potassium hydroxide powder, 30 g of PEG-400, and 0.3 g of 701 polymerization inhibitor to a reaction flask. Add 0.5 mol (83 g) of fluorene under stirring conditions, and add 0.4 mol of 2-chloromethylstyrene dropwise while stirring at 40°C under a nitrogen stream. React for 4.0 hours under stirring conditions of 350 r / min. Then, add 0.6 mol of 4-chloromethylstyrene dropwise while stirring, and continue stirring for 8.0 hours. Stop the reaction, evaporate the acetonitrile, add 500 mL of water and 500 mL of toluene, separate the layers, and extract the organic phase. The solid was washed with 500 mL of saturated ammonium chloride solution, washed with water until neutral, evaporated under reduced pressure using toluene, twice beaten with 500 mL of methanol (30°C), filtered, and the resulting solid was recrystallized twice with toluene. The resulting solid was vacuum-dried at 80°C until constant weight was obtained, yielding 106.6 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) as white crystals. The purity (HPLC) was 98.7% and the yield was 53.5%.

[0090] Example 8 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. After removing the solvent under reduced pressure, a thermosetting hydrocarbon resin was prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), and the glass transition temperature was measured. The prepared resin was fabricated into an 80 mm × 80 mm × 0.4 mm sheet, and the dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer. The results are shown in Table 4.

[0091] Example 9 Add 500 mL of acetonitrile, 1.4 mol of potassium tert-butoxide, 30 g of PEG-400, and 0.5 g of 701 polymerization inhibitor to a reaction flask. While stirring under a nitrogen stream, add 0.6 mol of fluorene and 1.4 mol of 4-vinylbenzyl chloride (HPLC, 99%). React under stirring conditions of 30-35°C and 350 r / min until the fluorene content is less than 1 wt% by HPLC analysis. Stop the reaction, evaporate the acetonitrile, add 500 mL of water and 500 mL of toluene, separate the layers, wash the organic phase with saturated ammonium chloride solution, and rinse with water three times until neutral. The mixture was washed (500 mL of water was used each time), toluene was evaporated under reduced pressure, a mixed solvent of toluene and methanol in a volume ratio of 1:0.3 was added, and the mixture was heated until completely dissolved. The temperature was then cooled to 5°C at a rate of 0.5°C / min and crystallized at constant temperature. The mixture was filtered, and the resulting solid component was dried at 90°C until constant weight was achieved to obtain 9,9-bis(2-vinylbenzyl)-9H-fluorene (p,p-BVBF) as white crystals. The melting point was 118.5~120.0°C, and the purity (HPLC) was 99.5%.

[0092] 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 the solvent was removed under reduced pressure. A thermosetting hydrocarbon resin was then prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), and the glass transition temperature was measured. The prepared resin was fabricated into an 80 mm × 80 mm × 0.4 mm sheet, and the dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer. The results are shown in Table 4.

[0093] Example 10 9,9-bis(2-vinylbenzyl)-9H-fluorene (p,p-BVBF) was prepared as white crystals according to the method of Example 9, with a melting point of 118.5-120.0°C and a purity (HPLC) of 99.5%. 10 g of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene(o,p-BVBF) and 10 g of 9,9-bis(4-vinylbenzyl)-9H-fluorene(p,p-BVBF) prepared in Example 1, along with 0.1 g of T311 peroxide initiator, were dissolved in 50 g of toluene. After removing the solvent under reduced pressure, a thermosetting hydrocarbon resin was prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min). The glass transition temperature was measured, and the prepared resin was fabricated into an 80 mm × 80 mm × 0.4 mm sheet. The dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer, and the results are shown in Table 4.

[0094] Example 11 In a 2L four-necked flask, add 150mL methanol, 0.09mol N,N-di-tert-butylethylenediamine, and 0.07mol copper bromide. Stir to dissolve, then introduce oxygen and continuously bubble. Maintain the temperature at 40-45°C and stir to allow the reaction to proceed. Add 1.0mol 2,6-dimethylphenol and 0.125mol tetramethylbisphenol A in a 500mL toluene / 150mL methanol mixture to the reaction flask dropwise. After the addition is complete, introduce oxygen and continue bubbling. Continue stirring at the same temperature for 4 hours to allow the reaction to proceed. After the reaction is complete, neutralize with 10% dilute hydrochloric acid until neutral, then add EDTA-2Na. Add 50 mL of an aqueous solution containing 7 g (0.04 mol) and stir for 30 min. Add 600 mL of methanol, filter the precipitate, beat and wash three times with 300 mL of methanol, and vacuum dry at 80°C for 8 hours to obtain 285.0 g of polyphenylene ether (XSPPO), with Mn = 1750 and Mw = 2030.

[0095] Add 120 mL of toluene to a 500 mL four-necked flask, add 60 g of polyphenylene ether (SXPPO), 60 mL of 50% sodium hydroxide solution, 4 g (0.043 mol) of tetrabutylammonium bromide, 0.1 g of 701 polymerization inhibitor, and 15 g (0.18 mol) of p-chloromethylstyrene, stir under nitrogen protection, raise the temperature to 70°C, stir for 8 hours to react, cool to room temperature, neutralize with 10% dilute hydrochloric acid, wash the organic phase three times with 200 mL of water, add to 800 mL of methanol, filter the precipitated precipitate, wash with methanol / water (weight ratio 80:20), and vacuum dry at 80°C for 8 hours to obtain 82 g of modified polyphenylene ether (XSmPPO), with Mn=1860 and Mw=2180. The structural formula of XSmPPO is as follows. [ka]

[0096] 4 g (0.01 mol) of 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) prepared in Example 1, 16 g of XSmPPO4, and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene. After removing the solvent under reduced pressure, a crosslinked resin was prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), and the glass transition temperature was measured. This crosslinked resin was fabricated into an 80 mm × 80 mm × 0.4 mm sheet, and the dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer. The results are shown in Table 4.

[0097] Example 12 9,9-bis(4-vinylbenzyl)-9H-fluorene (p,p-BVBF) was prepared according to the method of Example 9. Modified polyphenylene ether (XSmPPO) was prepared according to the method of Example 11. 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. After removing the solvent under reduced pressure, a crosslinked resin was prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), and the glass transition temperature was measured. This crosslinked resin was then fabricated into an 80 mm × 80 mm × 0.4 mm sheet, and the dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer. The results are shown in Table 4.

[0098] Example 13 9,9-bis(4-vinylbenzyl)-9H-fluorene (p,p-BVBF) was prepared according to the method of Example 9. Modified polyphenylene ether (XSmPPO) was prepared according to the method of Example 11. 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 XSmPPO4, and 0.1 g of T311 peroxide initiator were dissolved in 50 g of toluene. After removing the solvent under reduced pressure, a crosslinked resin was prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), and the glass transition temperature was measured. This crosslinked resin was fabricated into an 80 mm × 80 mm × 0.4 mm sheet, and the dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer. The results are shown in Table 4.

[0099] Comparative Example 1 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. After removing the solvent under reduced pressure, a thermosetting hydrocarbon resin was prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min). The glass transition temperature was measured, and this thermosetting hydrocarbon resin was fabricated into an 80 mm × 80 mm × 0.4 mm resin sheet. The dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer, and the results are shown in Table 4.

[0100] Comparative Example 2 Modified polyphenylene ether (XSmPPO) was prepared according to the method of Example 11. 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 under reduced pressure, a thermosetting resin was prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), and the glass transition temperature was measured. This resin was then fabricated into an 80 mm × 80 mm × 0.4 mm sheet, and the dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer. The results are shown in Table 4.

[0101] Comparative Example 3 Modified polyphenylene ether (XSmPPO) was prepared according to the method of Example 11. 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. After removing the solvent under reduced pressure, a crosslinked resin was prepared by melt casting (thermosetting conditions: temperature 220°C, pressure 70-80 mmHg, time 100 min), and the glass transition temperature was measured. This crosslinked resin was then fabricated into an 80 mm × 80 mm × 0.4 mm sheet, and the dielectric constant and dielectric loss tangent of the sample were measured at a frequency of 10 GHz using an Agilent N5230A vector network analyzer. The results are shown in Table 4.

[0102] [Table 4]

[0103] In Table 4, Dk is the dielectric constant, Df is the dielectric loss tangent, and Tg is the glass transition temperature. Table 4 shows that the thermosetting hydrocarbon resins prepared with 9,9-bis(4-vinylbenzyl)-9H-fluorene have very low dielectric loss tangents and fairly high glass transition temperatures (Examples 8, 9, 10). Among them, the thermosetting hydrocarbon resin prepared with 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene (o,p-BVBF) had the lowest dielectric loss tangent and the highest glass transition temperature (Example 8). Crosslinked resins 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 both (Example 13) with terminal vinyl-modified polyphenylene ether showed significantly lower dielectric constant, significantly lower dielectric loss tangent, and significantly higher glass transition temperature compared to crosslinked resins of 1,2-bis(4-vinylphenyl)ethane (BVPE), a common crosslinking agent, with terminal vinyl-modified polyphenylene ether (Comparative Example 3). Furthermore, the higher the weight percentage of o,p-BVBF used as the crosslinking agent, the lower the dielectric loss tangent and the higher the glass transition temperature. Therefore, the thermosetting hydrocarbon resins and thermosetting crosslinked resins with modified polyphenylene ethers of the present invention have excellent overall performance and can be used as resin materials for high-frequency, high-speed printed circuit boards.

[0104] Although the above embodiments have described the present invention in detail, they represent only a portion of the present invention, not all embodiments, and other embodiments can be obtained based on these embodiments without any creativity, and all of these embodiments fall within the scope of protection of the present invention.

Claims

1. Asymmetric bisvinylbenzylfluorene, 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene having the structure shown in formula 1, 【Chemistry 14】 Thermal analysis of the aforementioned 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene revealed a melting endothermic peak at 169-175°C, indicating a monoclinic crystal system and a space group P2. １ An asymmetrical bisvinylbenzylfluorene characterized by being / c.

2. A method for preparing asymmetric bisvinylbenzylfluorene according to claim 1, The steps include: mixing fluorene, an alkaline reagent, a polymerization inhibitor, and a polar aprotic solvent to obtain a fluorene-containing mixture; A preparation method characterized by comprising the step of sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing mixed system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing mixed system to carry out a nucleophilic substitution reaction to obtain the asymmetric bisvinylbenzylfluorene.

3. The alkaline reagent comprises one or more of the following: alkali metal hydroxide, alkali metal alkoxide, sodium hydride, and potassium hydride. The polymerization inhibitor comprises one or more of the following: nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide. The aforementioned polar aprotic solvent includes dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, or hexamethylphosphoramide. The molar ratio of fluorene to alkaline reagent is 1:1.8 to 5. The molar ratio of 2-vinylbenzyl chloride to 4-vinylbenzyl chloride is 2 to 6:4 to 8. The method for preparing asymmetric bisvinylbenzylfluorene according to claim 2, characterized in that the molar ratio of the total molar amount of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to fluorene is 1.8 to 2.2:

1.

4. The method for preparing asymmetric bisvinylbenzylfluorene according to claim 2 or 3, characterized in that the temperature of the nucleophilic substitution reaction is 20 to 50°C and the time is 2 to 8 hours.

5. A method for preparing asymmetric bisvinylbenzylfluorene according to claim 1, The steps include: mixing fluorene, an alkaline reagent, a polymerization inhibitor, a phase transfer catalyst, and a solvent to obtain a fluorene-containing phase transfer catalyst system; A preparation method characterized by comprising the steps of sequentially adding 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing phase-transfer catalyst system, or adding a mixed solution of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride dropwise to the fluorene-containing phase-transfer catalyst system, carrying out a nucleophilic substitution reaction under phase-transfer catalyst conditions to obtain the asymmetric bisvinylbenzylfluorene.

6. The alkaline reagent comprises alkali metal hydroxides and / or alkali metal alkoxides. The polymerization inhibitor comprises one or more of the following: nitromethane, nitrobenzene, o-nitrophenol, phenothiazine, 2-phenylnaphthylamine, hydroquinone, catechol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, p-tert-butylcatechol, 2,2,6,6-tetramethylpiperidine nitrogen oxide, and 2,2,6,6-tetramethyl-4-hydroxypiperidine nitrogen oxide. The phase transfer catalyst comprises one or more of the following: a quaternary ammonium salt, a quaternary phosphonium salt, and polyethylene glycol. The mass of the phase transfer catalyst is 5 to 25% of the mass of fluorene. The molar ratio of fluorene to alkaline reagent is 1:1.8 to 5. The molar ratio of 2-vinylbenzyl chloride to 4-vinylbenzyl chloride is 2 to 6:4 to 8. The method for preparing asymmetric bisvinylbenzylfluorene according to claim 5, characterized in that the total molar amount of 2-vinylbenzyl chloride and 4-vinylbenzyl chloride to the molar ratio of fluorene is 1.8 to 2.2:

1.

7. The method for preparing asymmetric bisvinylbenzylfluorene according to claim 5 or 6, characterized in that the temperature of the nucleophilic substitution reaction under the phase transfer catalyst conditions is 25 to 75°C and the duration is 8 to 18 hours.

8. A thermosetting resin comprising a thermosetting hydrocarbon resin and / or a thermosetting crosslinked resin, wherein the thermosetting hydrocarbon resin comprises a thermosetting hydrocarbon resin prepared using 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene as a raw material and / or 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, The thermosetting crosslinked resin comprises a thermosetting crosslinked resin prepared 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 represented by any one of formulas 2 to 5. 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] The thermosetting resin is characterized in that the 9-(2-vinylbenzyl)-9'-(4-vinylbenzyl)-9H-fluorene is the asymmetric bisvinylbenzylfluorene described in claim 1 or the asymmetric bisvinylbenzylfluorene prepared by the preparation method described in claim 2.

9. A method for preparing a thermosetting resin according to claim 8, The steps include: dissolving the raw materials and initiator in toluene to obtain a mixed solution; A preparation method characterized by comprising the step of removing toluene from the mixed solution, and then performing melt heat curing to obtain the thermosetting resin.

10. A resin material for high-frequency, high-speed substrates, using the thermosetting resin described in claim 8.

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