Benzocyclobutene-substituted bisphenol fluorene, and synthesis method and application thereof

Abstract

The application discloses a benzocyclobutene-substituted bisphenol fluorene and a synthesis method and application thereof. The application uses commercially available 4-bromobenzocyclobutene and commercially available or laboratory-prepared 9,9-bisphenol-substituted fluorene compounds as raw materials, uses monovalent cuprous inorganic salt as a catalyst, and uses simple oxalic diamide compounds as ligands, and then the benzocyclobutene-substituted bisphenol fluorene is obtained in a suitable base and an organic solvent with a high yield. The synthesis method has the characteristics of simple operation, high raw material utilization rate and easy purification and separation, realizes efficient substitution of the benzocyclobutene group on the bisphenol fluorene phenolic hydroxyl group, and has the application prospect suitable for large-scale preparation.

Description

Technical Field

[0001] This invention belongs to the field of organic compound process synthesis and application technology and high-performance thermosetting resin monomers. Specifically, it relates to a benzocyclobutene-substituted bisphenol fluorene and its synthesis method and application. This type of compound can be used as a functional monomer for low dielectric, high heat resistance, high dimensional stability resins, electronic packaging materials, copper clad laminate resins, or optoelectronic materials. Background Technology

[0002] The International Devices and Systems Roadmap proposes that integrated circuit dielectric materials should achieve a dielectric constant (D) below 2.0 by 2028. k ), and by 2030, dielectric loss (D f The concentration of benzocyclobutene (BCB) resin is reduced to below 0.002 to address issues such as signal transmission delay and electromagnetic interference in high-density integrated circuits. This is due to its excellent overall properties, including outstanding thermal stability (glass transition temperature T0). g >400℃), low moisture absorption (water absorption <0.2%) and dielectric properties (D k =2.65, D f = 0.0008), showing great application potential in 5G millimeter-wave packaging materials and flexible electronics. Benzocyclobutene can undergo cyclobutene ring-opening upon heating to generate active o-quinone dimethane ( o-QDM) intermediates can further undergo self-polymerization reactions; during this curing process, small molecules are usually not released, and a highly cross-linked network is formed after curing. Studies have shown that reducing molecular polarizability is beneficial to reducing dielectric constant; while introducing rigid aromatic structures at the molecular scale can achieve a lower molecular polarizability. 9,9-Bisphenol-substituted fluorene compounds, due to the presence of a rigid fluorene ring and two phenolic hydroxyl groups in their molecular structure, have the following advantages: 1) The fluorene ring structure is highly rigid, which is beneficial to improving the glass transition temperature and heat resistance of the polymer; 2) The high content of aromatic structures is beneficial to improving thermal stability and mechanical strength; 3) The fluorene structure has a large volume, which can increase the molecular free volume and, to some extent, is beneficial to reducing the dielectric constant of the material; 4) The bisphenol functional group has good reactivity, and bisphenol fluorene derivatives can be obtained through further etherification, esterification, alkylation and other reactions, which can be used as structural units for high-performance materials such as epoxy resins, polycarbonates, polyarylene ethers, polyimides, and benzoxazine resins. Therefore, introducing thermally crosslinkable benzocyclobutene groups using 9,9-bisphenol fluorene as the parent compound is an important method for constructing resin monomers with low dielectric constant, high heat resistance, low water absorption, and high dimensional stability. Existing technologies have reported the preparation of thermosetting resin monomers by combining fluorene and benzocyclobutene structural units. In 2013, patent CN103086851B disclosed thermosetting resin monomers containing fluorene and benzocyclobutene structural units. These monomers can be formed into films through casting, spin coating, or drop coating, and then cured by staged temperature increases to obtain highly crosslinked thermosetting resins or films. Existing technologies have disclosed methods for preparing benzocyclobutene-substituted bisphenol fluorene compounds, but there is still room for improvement in their reaction yield. For these functional monomers, the target product usually needs to be purified before use in subsequent resin or electronic material preparation. If the reaction yield is not high enough, it will not only waste raw materials but also increase the burden of byproduct separation and post-processing. Therefore, it is still necessary to further optimize existing synthesis processes to obtain preparation methods with higher yields and better process stability. This invention provides an improved preparation method for benzocyclobutene-substituted bisphenol fluorene compounds. Based on existing reaction routes, by adjusting catalysts, ligands, solvents, and reaction temperatures, the separation yield of the target product is improved. Compared with existing methods, the method of this invention can achieve higher yields in the same or similar substrate systems, reduce raw material losses and by-product formation, and has good process application value. Experimental results show that, under the same substrate and feed ratio, the separation yield of the target product using existing methods is approximately 55% (CN103086851B); the separation yield of the target product using the method of this invention can reach approximately 85%, an improvement of approximately 30%-35% compared to existing methods. Simultaneously, the residual carbon content (800℃) of the thermosetting resin obtained using the method of this invention is increased by approximately 10% compared to existing methods, exhibiting better heat resistance; and the dielectric constant (1 MHz) is increased by approximately 20% compared to existing methods, better meeting the signal transmission requirements of integrated circuits. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the primary objective of this invention is to provide a method for synthesizing benzocyclobutene-substituted bisphenol fluorene. This invention utilizes commercially available 4-bromobenzocyclobutene and commercially available or laboratory-prepared 9,9-bisphenol-substituted fluorene compounds as raw materials, a monovalent cuprous inorganic salt as a catalyst, and easily prepared oxalyldiamine compounds as ligands. The reaction is carried out in suitable alkalis and organic solvents to obtain benzocyclobutene-substituted bisphenol fluorene in high yield. The synthesis method of this invention is characterized by its simplicity, high raw material utilization, and ease of purification and separation. It achieves efficient substitution of the phenolic hydroxyl group of bisphenol fluorene by the benzocyclobutene group, and has promising applications suitable for large-scale preparation.

[0004] A second objective of this invention is to provide benzocyclobutene-substituted bisphenol fluorene prepared by the above-described synthetic method.

[0005] A third objective of this invention is to provide an application of benzocyclobutene-substituted bisphenol fluorene in the preparation of thermosetting resin materials.

[0006] The present invention adopts the following technical solution: In a first aspect, the present invention provides a method for synthesizing benzocyclobutene-substituted bisphenol fluorene, comprising the following steps: at room temperature, mixing and reacting a 9,9-bisphenol-substituted fluorene compound, 4-bromobenzocyclobutene, a copper catalyst, a ligand, a base, and an organic solvent I, and then further processing the resulting product to obtain benzocyclobutene-substituted bisphenol fluorene.

[0007] The molar ratio of the 9,9-bisphenol-substituted fluorene compound to 4-bromobenzocyclobutene is 1:2~5; the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the copper catalyst is 1:0.05~0.4; the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the ligand is 1:0.1~0.8; and the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the base is 1:2~5.

[0008] The base is a metal hydroxide, a metal carbonate, a metal tert-butoxide, or a metal phosphate.

[0009] Preferably, the 9,9-bisphenol-substituted fluorene compound is one of 9,9-bis(4-hydroxyphenyl)fluorene, 6,6-(9H-fluorene-9,9-diyl)bis(naphthyl-2-phenol), and 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene.

[0010] Preferably, the copper catalyst is one of cuprous chloride, cuprous bromide, and cuprous iodide.

[0011] Preferably, the ligand is N1 , N2 -bis(furan-2-ylmethyl)oxalamide,N1 , N2 -bis(thiophen-2-ylmethyl)oxalamide, N1 , N2 -Dibenzyl oxalamide or N1 , N2 One of the following: bis((1,1'-biphenyl)-2-yl)oxalamide.

[0012] Preferably, the alkali is one of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, or potassium phosphate.

[0013] Preferably, the organic solvent I is N , N -Dimethylformamide, N N-Dimethylacetamide, dimethyl sulfoxide, N At least one of 1,4-dioxane, toluene, xylene, or mesitylene.

[0014] Preferably, the reaction temperature is 60~150 ℃ and the reaction time is 12~48 h; the reaction is carried out in an air, nitrogen or argon atmosphere.

[0015] More preferably, the reaction temperature is 135 °C and the reaction time is 12 h.

[0016] More preferably, the molar ratio of the 9,9-bisphenol-substituted fluorene compound to 4-bromobenzocyclobutene is 1:3.5~5; the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the copper catalyst is 1:0.15~0.25; the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the ligand is 1:0.3~0.5; and the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the base is 1:3.5~5.

[0017] Preferably, the subsequent treatment refers to quenching the reaction, extracting the reaction solution with organic solvent II, separating the aqueous layer, drying the organic layer with a desiccant, filtering, and removing organic solvent II by rotary evaporation under reduced pressure to obtain a crude product, which is then purified by recrystallization to obtain benzocyclobutene-substituted bisphenol fluorene.

[0018] Preferably, the quenching reaction refers to the addition of pure water to the reaction system; the organic solution II is one of ethyl acetate, dichloromethane, chloroform, or n-hexane; and the desiccant is at least one of anhydrous sodium sulfate or anhydrous magnesium sulfate.

[0019] Preferably, the recrystallization purification refers to using ethyl acetate or dichloromethane as a good solvent and n-hexane or petroleum ether as a poor solvent, dissolving the crude product in a certain amount of good solvent, and precipitating the pure product in 10 to 40 times its volume of poor solvent.

[0020] More preferably, the recrystallization purification refers to using dichloromethane as a good solvent and petroleum ether as a poor solvent, dissolving the crude product in a certain amount of good solvent, and precipitating the pure product in 15 to 25 times its volume of poor solvent.

[0021] Secondly, the present invention provides a benzocyclobutene-substituted bisphenol fluorene, which is prepared by the above method.

[0022] Preferably, the benzocyclobutene-substituted bisphenol fluorene has the following structural formula:

[0023] Among them, R 1 R 2 Each can be independently H, CH3, or phenyl; R 1 R 2 They can be the same or different.

[0024] Thirdly, this invention provides an application of benzocyclobutene-substituted bisphenol fluorene in the preparation of thermosetting resin materials. The benzocyclobutene-substituted bisphenol fluorene is dissolved in organic solvent III to prepare a solution, which is then uniformly coated onto a polytetrafluoroethylene mold. After natural drying to allow most of the organic solvent III to evaporate, the solution is cured by staged heating to obtain a highly crosslinked thermosetting resin.

[0025] Preferably, the organic solution III is dichloromethane, trichloromethane, 1,4-dioxane, butanone-2-one, toluene, dimethyl sulfoxide, etc. N , N At least one of dimethylformamide.

[0026] Preferably, the staged heating and curing procedure is as follows: pretreatment at 150~170 ℃ for 0.5~2 h, heat curing at 190~230 ℃ for 2~8 h, and heat treatment at 230~250 ℃ for 1~4 h.

[0027] Preferably, the heating and curing process is carried out under air, nitrogen, or negative pressure (0.09 MPa); more preferably, the heating and curing process is carried out under negative pressure (0.09 MPa).

[0028] The cross-linked self-polymer insoluble and infusible resin material obtained after curing has good heat resistance and dimensional stability, high chemical stability and high glass transition temperature, and can be used in low dielectric resins, electronic packaging materials, high frequency insulating materials or copper clad laminate resins, etc.

[0029] Advantages and benefits of this invention: 1. Under the same substrate and feed ratio, the target product separation yield is about 55% using the method described in CN103086851B; by using the copper catalyst and ligand described in this invention, combined with recrystallization purification, the target product separation yield can reach 85%.

[0030] 2. The residual carbon rate (800 °C) of the thermosetting resin obtained by the method of the present invention is about 10% higher than that of the product in the previously reported patent CN103086851B, and it has better heat resistance; and its dielectric constant (1 MHz) is about 20% higher than that of the product in the previously reported patent CN103086851B, which can better meet the signal transmission requirements of integrated circuits. Attached Figure Description

[0031] Figure 1 The 1H NMR spectrum of 9,9-bis[6-(benzocyclobuten-4-yloxy)-2-naphthyl]fluorene synthesized in Example 2 is shown.

[0032] Figure 2 Thermogravimetric analysis (TGA) diagram of the thermosetting resin prepared in Example 5. Detailed Implementation Plan The implementation of the present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments of the present invention are not limited thereto. It should be noted that any processes or parameters not specifically described in detail below are those that can be understood or implemented by those skilled in the art with reference to the prior art.

[0033] I. Synthetic methods of benzocyclobutene-substituted bisphenol fluorene Example 19. Synthesis of 9-bis(4-benzocyclobutenylphenyl ether)fluorene The method for preparing benzocyclobutene-substituted bisphenol fluorene is as follows: Under a nitrogen atmosphere, 3.5 g of 9,9-bis(4-hydroxyphenyl)fluorene, 7.3 g of 4-bromobenzocyclobutene, 0.381 g of cuprous iodide, and 1.2 g of... were added to a 100 mL two-necked flask equipped with a spherical reflux condenser. N1 , N2 - Dibenzyl oxalamide, 13.0 g cesium carbonate and 25 ml N , NThe reaction system of 9,9-dimethylformamide was stirred at 135°C for 12 hours. Stirring was stopped, and the reaction was quenched with purified water. Ethyl acetate was added to extract the reaction solution, and the ethyl acetate layer was dried over anhydrous sodium sulfate, filtered, and then evaporated under reduced pressure to remove the solvent. The product was then purified by recrystallization. The good solvent used for recrystallization was dichloromethane, and the poor solvent used was petroleum ether, with a volume ratio of 1:20. The obtained 9,9-bis(4-benzocyclobutenylphenyl ether)fluorene was a white or colorless solid, with a yield of 84%.

[0034] The structural characterization data of the product obtained in this embodiment are shown below: 1 H NMR (400 MHz, CDCl3) δ 7.74 (d, J = 6.0 Hz, 2H), 7.38 (d, J = 6.0 Hz, 2H), 7.34 (t, J = 6.0 Hz, 2H), 7.26 (t, J = 6.0 Hz, 2H), 7.12 (d, J = 6.0 Hz, 4H), 6.96 (d, J = 5.6 Hz, 2H), 6.83 (d, J = 6.0 Hz, 2H), 6.79 (d, J = 7.2 Hz, 4H), 6.71 (s, 2H), 3.10 (s, 8H). 13 C NMR(101 MHz, CDCl3) δ 157.0, 156.0, 151.5, 146.7, 140.6, 140.0,140.0, 129.3, 127.7, 127.5, 126.1, 123.8, 120.2, 118.7, 117.6, 114.7, 64.4,29.1, 28.9. IR(KBr): 3077, 2970, 1501, 1464, 1233, 1067, 744. Example 29, Synthesis of 9-bis[6-(benzocyclobuten-4-yloxy)-2-naphthyl]fluorene The method for preparing benzocyclobutene-substituted bisphenol fluorene is as follows: Under a nitrogen atmosphere, 4.5 g of 6,6-(9H-fluorene-9,9-diyl)bis(naphthyl-2-phenol), 7.3 g of 4-bromobenzocyclobutene, 0.381 g of cuprous iodide, and 1.2 g of... were added to a 100 mL two-necked flask equipped with a spherical reflux condenser. N1 , N2 - Dibenzyl oxalamide, 13.0 g cesium carbonate and 25 ml N , N The reaction system of 9,9-dimethylformamide was stirred at 135°C for 12 hours. Stirring was stopped, and the reaction was quenched with purified water. Ethyl acetate was added to extract the reaction solution, and the ethyl acetate layer was dried over anhydrous sodium sulfate, filtered, and then evaporated under reduced pressure to remove the solvent. The product was then purified by recrystallization. The good solvent used for recrystallization was dichloromethane, and the poor solvent used was petroleum ether, with a volume ratio of 1:20. The obtained 9,9-bis[6-(benzocyclobuten-4-yloxy)-2-naphthyl]fluorene was a white or colorless solid, with a yield of 91%.

[0035] The structural characterization data of the product obtained in this embodiment are shown below: The proton NMR spectrum is shown below. Figure 1 As shown.

[0036] 1 H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 6.0 Hz, 2H), 7.63 (t, J = 6.0 Hz, 6H), 7.55 (d, J = 7.2 Hz, 2H), 7.44 (t, J = 7.2 Hz, 4H), 7.33 (t, J = 7.2 Hz, 2H), 7.12 (t, J = 7.2 Hz, 4H), 7.06 (d, J = 8.0 Hz, 2H), 6.94 (d, J = 8.0 Hz, 2H), 6.82 (s, 2H), 3.19 (s, 8H). 13C NMR(101 MHz, CDCl3) δ 156.2, 151.1, 146.9, 141.7, 140.8, 140.3,133.2, 129.9, 129.6, 127.9, 127.8, 127.7, 127.3, 126.3, 126.0, 124.0, 120.4,119.9, 118.8, 114.7, 112.8, 65.5, 29.1, 29.0. IR(KBr): 3058, 2926, 1595, 1463, 1225, 1160, 739. Example 3 Synthesis of 9,9-bis(3-methyl-4-benzocyclobutenylphenyl ether)fluorene The method for preparing benzocyclobutene-substituted bisphenol fluorene is as follows: Under a nitrogen atmosphere, 3.8 g of 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene, 7.3 g of 4-bromobenzocyclobutene, 0.381 g of cuprous iodide, and 1.2 g of... were added to a 100 mL two-necked flask equipped with a spherical reflux condenser. N1 , N2 - Dibenzyl oxalamide, 13.0 g cesium carbonate and 25 ml N , N The reaction system of 9,9-dimethylformamide was stirred at 135°C for 12 hours. Stirring was stopped, and the reaction was quenched with purified water. Ethyl acetate was added to extract the reaction solution, and the ethyl acetate layer was dried over anhydrous sodium sulfate, filtered, and then evaporated under reduced pressure to remove the solvent. The product was then purified by recrystallization. The good solvent used for recrystallization was dichloromethane, and the poor solvent used was petroleum ether, with a volume ratio of 1:20. The obtained 9,9-bis(3-methyl-4-benzocyclobutenylphenylether)fluorene was a white or colorless solid, with a yield of 80%.

[0037] The structural characterization data of the product obtained in this embodiment are shown below: 1 H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.0 Hz, 2H), 7.32-7.50 (m, 6H), 6.89-7.08 (m, 6H), 6.46-6.82 (m, 6H), 3.14 (s, 8H), 2.19 (s, 6H). 13C NMR(101 MHz, CDCl3) δ 157.0, 154.2, 151.6, 146.6, 140.8, 140.1,139.6, 130.8, 128.9, 127.7, 127.4, 126.9, 126.3, 123.7, 120.2, 118.2, 117.3,113.2, 64.5, 29.1, 28.9, 16.5. IR(KBr): 3058, 2925, 1493, 1464, 1249, 1157, 742. II. Application of Benzocyclobutene-substituted Bisphenol Fluorene in the Preparation of Thermosetting Resin Materials Example 4 Dissolve 0.5 g of 9,9-bis(4-benzocyclobutenylphenyl ether)fluorene in 2.5 mL of dichloromethane to prepare a solution. Coat the solution evenly in a 5 cm × 5 cm × 1 cm polytetrafluoroethylene mold and place it in a ventilated place for 1 day. After most of the dichloromethane has dried and evaporated naturally, place it in a vacuum oven and cure it in stages by heating: 160℃ for 0.5 hours, 220℃ for 3 hours, and 240℃ for 2 hours. After curing, a highly cross-linked thermosetting resin is obtained.

[0038] Example 5 0.5 g of 9,9-bis[6-(benzocyclobuten-4-yloxy)-2-naphthyl]fluorene was dissolved in 2.5 mL of dichloromethane to prepare a solution. This solution was evenly coated onto a 5 cm × 5 cm × 1 cm polytetrafluoroethylene mold and placed in a ventilated area for one day. After most of the dichloromethane had naturally dried and evaporated, the mold was placed in a vacuum oven for staged temperature increase curing: 160 °C for 0.5 hours, 220 °C for 3 hours, and 240 °C for 2 hours. The resulting highly cross-linked thermosetting resin was obtained. The thermogravimetric analysis (TGA) of the obtained thermosetting resin is shown below. Figure 2 As shown, the sample exhibits virtually no significant mass loss below approximately 450 °C, indicating a low volatile content and good thermal stability. Thermal decomposition begins around 450 °C, with the main weight loss occurring within the 470-570 °C range, exhibiting a single, rapid weight loss phase. The 5% thermogravimetric loss temperature is approximately 478.6 °C. At 700 °C, the sample retains 50.8% of its carbon, demonstrating high char-forming ability. This may be attributed to the high aromatic content in the thermosetting resin material and the dense three-dimensional cross-linked network formed after curing.

[0039] Example 6 Dissolve 0.5 g of 9,9-bis(3-methyl-4-benzocyclobutenylphenyl ether)fluorene in 2.5 mL of dichloromethane to prepare a solution. Coat the solution evenly in a 5 cm × 5 cm × 1 cm polytetrafluoroethylene mold and place it in a ventilated place for 1 day. After most of the dichloromethane has dried and evaporated naturally, place it in a vacuum oven and cure it in stages by heating: 160℃ for 0.5 hours, 220℃ for 3 hours, and 240℃ for 2 hours. After curing, a highly cross-linked thermosetting resin is obtained.

[0040] The thermodynamic properties of the thermosetting resins prepared in Examples 4, 5, and 6 were tested, and the specific results are shown in the table below: Table 1

[0041] As can be seen from the data comparison in Table 1, the residual carbon rate (800 °C) of the thermosetting resin obtained by the method of the present invention is about 10% higher than that of the product in the previously reported patent CN103086851B, which has better heat resistance; and its dielectric constant (1 MHz) is about 20% higher than that of the product in the previously reported patent CN103086851B, which can better meet the signal transmission requirements of integrated circuits.

Claims

1. A method for synthesizing benzocyclobutene-substituted bisphenol fluorene, characterized in that, The process includes the following steps: at room temperature, a 9,9-bisphenol-substituted fluorene compound, 4-bromobenzocyclobutene, a copper catalyst, a ligand, a base, and organic solvent I are mixed and reacted. The resulting product is then processed to obtain benzocyclobutene-substituted bisphenol fluorene.

2. The method for synthesizing benzocyclobutene-substituted bisphenol fluorene according to claim 1, characterized in that, The 9,9-bisphenol-substituted fluorene compound is one of 9,9-bis(4-hydroxyphenyl)fluorene, 6,6-(9H-fluorene-9,9-diyl)bis(naphthyl-2-phenol), and 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene.

3. The method for synthesizing benzocyclobutene-substituted bisphenol fluorene according to claim 1, characterized in that, The copper catalyst is one of cuprous chloride, cuprous bromide, and cuprous iodide.

4. The method for synthesizing benzocyclobutene-substituted bisphenol fluorene according to claim 1, characterized in that, The ligand is N1 , N2 -bis(furan-2-ylmethyl)oxalamide, N1 , N2 -bis(thiophen-2-ylmethyl)oxalamide, N1 , N2 -Dibenzyl oxalamide or N1 , N2 One of the following: bis((1,1'-biphenyl)-2-yl)oxalamide.

5. The method for synthesizing benzocyclobutene-substituted bisphenol fluorene according to claim 1, characterized in that, The alkali is one of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, or potassium phosphate.

6. The method for synthesizing benzocyclobutene-substituted bisphenol fluorene according to claim 1, characterized in that, The organic solvent I is N , N -Dimethylformamide, N N-Dimethylacetamide, dimethyl sulfoxide, N At least one of 1,4-dioxane, toluene, xylene, or mesitylene.

7. The method for synthesizing benzocyclobutene-substituted bisphenol fluorene according to claim 1, characterized in that, The reaction temperature is 60~150 ℃, and the reaction time is 12~48 h; the reaction is carried out in an air, nitrogen or argon atmosphere.

8. The method for synthesizing benzocyclobutene-substituted bisphenol fluorene according to claim 1, characterized in that, The molar ratio of the 9,9-bisphenol-substituted fluorene compound to 4-bromobenzocyclobutene is 1:2~5; the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the copper catalyst is 1:0.05~0.4; the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the ligand is 1:0.1~0.8; and the molar ratio of the 9,9-bisphenol-substituted fluorene compound to the base is 1:2~5.

9. The benzocyclobutene-substituted bisphenol fluorene obtained by the synthetic method according to any one of claims 1-8, characterized in that, The structural formula of the benzocyclobutene-substituted bisphenol fluorene is as follows: Among them, R 1 R 2 Each can be independently H, CH3, or phenyl; R 1 R 2 They can be the same or different.

10. The application of the benzocyclobutene-substituted bisphenol fluorene according to claim 9 in the preparation of thermosetting resin materials, characterized in that, By dissolving the benzocyclobutene-substituted bisphenol fluorene in organic solution III to prepare a solution, uniformly coating it in a polytetrafluoroethylene mold, and allowing most of the organic solution III to evaporate naturally, the resin is cured by staged heating to obtain a highly cross-linked thermosetting resin. The organic solution III is dichloromethane, trichloromethane, 1,4-dioxane, butanone-2-one, toluene, dimethyl sulfoxide, N , N At least one of dimethylformamide; The staged heating and curing procedure is as follows: pretreatment at 150~170 ℃ for 0.5~2 h, heat curing at 190~230 ℃ for 2~8 h, and heat treatment at 230~250 ℃ for 1~4 h; The heating and curing process is carried out under air, nitrogen, or negative pressure conditions.

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