Synthesis method of high-purity benzocyclobutenyl organosilicon monomer for semiconductor packaging resin

Abstract

The invention discloses a synthesis method of a high-purity benzocyclobutenyl organosilicone monomer for semiconductor packaging resin, which specifically comprises the following steps: by taking vinyl silane and 4-bromobenzocyclobutene as reaction raw materials, firstly preparing benzocyclobutene-vinyl silane through Heck reaction, and then preparing benzocyclobutene-vinyl silane by taking a Meerwein reagent as a medium and potassium carbonate as an additive, thereby obtaining the high-purity benzocyclobutenyl organosilicone monomer for semiconductor packaging resin. And carrying out mild reaction in a polar aprotic solvent to directly prepare the high-purity benzocyclobutene organic silicon monomer tetramethyl divinyl siloxane dibenzocyclobutene. Compared with the traditional preparation method, the method has the advantages of wide reaction raw material source, low price, few reaction steps and high yield in synthesis, and the reaction is beneficial to the high purification process of the monomer, so that the method is more suitable for industrial batch production.

Description

Technical Field

[0002] This invention relates to the field of organic chemistry, and more specifically to a method for synthesizing a high-purity benzocyclobutene-based organosilicon monomer for semiconductor encapsulation resins. Background Technology

[0003] Benzocyclobutene-based resins (BCB resins) are a class of high-performance thin-film polymers that undergo rapid ring-opening crosslinking reactions at temperatures above 220°C. No small molecules are released during the curing process, resulting in thermosetting resins with low dielectric constant (Dk=2.65), low dielectric loss (Df=0.0005), high elastic modulus (2.2 GPa), and low moisture absorption (<0.1%). Currently, BCB resins are widely used in advanced semiconductor packaging technologies, including 2.5D / 3D semiconductor packaging, TSV (Through Silicon Viaduct) stacked memory, WL-CSP (Wafer Level Chip Scale Packaging), FOWLP / FOPLP (Fan-Out / Flat Panel Level Packaging), and the formation of fine redistribution layers (RDLs) on silicon intercalations.

[0004] Currently, tetramethyldivinylsiloxane bisbenzocyclobutene (DVS-bis-BCB) is the core organosilicon monomer of BCB resin. Dow Chemical Company reported two main methods for its synthesis in its published patents in 1989 and 1996 (US Pat. No. 4,812,588 and US Pat. No. 5,567,835): Alan K. Schrock's method, which involves the Heck coupling reaction of 4-bromobenzocyclobutene and tetramethyldivinylsiloxane (DVS) under palladium catalysis to prepare DVS-bis-BCB; and Robert A. DeVries' method, which involves first preparing 4-ethynylbenzocyclobutene from 4-bromobenzocyclobutene, then performing a hydrosilylation reaction of dimethylchlorosilane and 4-ethynylbenzocyclobutene under chloroplatinic acid hexahydrate catalysis, and finally undergoing a polycondensation reaction in an ice-water bath to prepare DVS-bis-BCB. In Alan K. Schrock's synthesis method, firstly, tetramethyldivinylsiloxane is not an easily obtained raw material and is relatively expensive; secondly, byproducts account for as much as 15-25% of the reaction process, and the crude product must undergo repeated peroxide and purification treatments to eliminate phosphine ligands, halogens, and palladium used in the reaction to a certain extent. However, due to the high viscosity of DVS-bis-BCB, the removal of phosphine ligands becomes extremely difficult (the presence of phosphine may cause unnecessary side reactions during resin use, leading to abnormal dissolution or shedding of the resin during development or etching, reducing the process window, such as exposure latitude and depth of focus); finally, after complex post-processing, the obtained DVS-bis-BCB is still a mixture of isomers, including the trans / trans type, which is the main component, and a small amount of trans / gem type isomers. In Robert A. DeVries' synthetic method, 4-bromobenzocyclobutene and trimethylsilylacetylene are first used as reactants. An intermediate containing acetylenylsilane is obtained under the catalysis of palladium dichloride, triphenylphosphine, and cuprous iodide. This intermediate is then dehydrated with a methanol solution of potassium carbonate to obtain 4-acetylenylbenzocyclobutene. This reaction route is lengthy and yields low amounts. Compared to Alan K. Schrock's method, Robert A. DeVries' synthetic method improves the overall yield of DVS-bis-BCB to some extent due to the reduction in byproduct content. However, trans / trans type (85.8% by mass), trans / gem type (9.1% by mass), and unknown isomers (5.1% by mass) still exist. During the reaction, the introduction of metal catalysts, phosphine ligands, and even chloride ions complicates the high-purity process of DVS-bis-BCB, and the multi-step method also increases the synthesis cost of the monomer.Therefore, it is particularly important to develop a method for synthesizing high-purity DVS-bis-BCB monomers. Summary of the Invention

[0005] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0006] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art: to provide a method for synthesizing high-purity benzocyclobutene organosilicon monomer for semiconductor encapsulation resin. The method has a simple route, high synthesis yield, low cost, high purity and is suitable for mass production.

[0007] To achieve these objectives and other advantages according to the present invention, a method for synthesizing a high-purity benzocyclobutene-based organosilicon monomer for semiconductor encapsulation resin is provided, comprising the following steps: Step 1: Using vinylsilane as a raw material, react with 4-bromobenzocyclobutene in the presence of a metal catalyst, an organophosphine ligand, an organic amine, and a first solvent. After the reaction is complete, the mixture is vacuum filtered, filtered with silica gel, concentrated, and distilled to obtain benzocyclobutene-vinylsilane. Step 2: Benzocyclobutene-vinylsilane undergoes a condensation reaction in the presence of Meerwein reagent, inorganic base, and a second solvent. After the reaction is complete, the mixture is filtered, washed with water, extracted with a third solvent, washed with saturated brine, dried with a desiccant, filtered, and concentrated to obtain high-purity benzocyclobutene-based organosilicon monomer DVS-bis-BCB for semiconductor encapsulation resin.

[0008] Preferably, the vinyl silane is any one of vinyl dimethyl methoxysilane, vinyl dimethyl ethoxysilane, vinyl dimethyl propoxysilane, vinyl dimethyl isopropoxysilane, and vinyl dimethyl tert-butoxysilane.

[0009] Preferably, the metal catalyst is one or more of palladium chloride, palladium acetate, palladium dichloride of bis(triphenylphosphine)phosphine, palladium tetra(triphenylphosphine)phosphine, palladium dibenzylacetone of bis(dibenzyl)acetone, palladium trifluoroacetate, palladium nitrate, palladium dichloride of [1,1′-bis(diphenylphosphine)ferrocene], and palladium on carbon.

[0010] Preferably, the organophosphine ligand is one or more of the following: diphenylphosphine, dicyclohexylphosphine, bis(diphenylphosphine)methane, bis(diphenylphosphine)ethane, bis(diphenylphosphine)propane, bis(diphenylphosphine)butane, bis(diphenylphosphine)pentane, bis(diphenylphosphine)benzene, bis(diphenylphosphine)naphthalene, triphenylphosphine, tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, tris(o-methylphenyl)phosphine, tris(2-furanyl)phosphine, 1,3,5-triaza-7-phosphaadamantane, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 1,2-bis(dicyclohexylphospho)ethane, and 1,1'-bis(di-tert-butylphosphine)ferrocene.

[0011] Preferably, the organic amine is one or more of triethylamine, tri-n-butylamine, isopropyl diethylamine, cyclohexyl diethylamine, tetramethylguanidine, and 1,4-diazabicyclo[2.2.2]octane.

[0012] Preferably, the first solvent is one or more of toluene, dioxane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.

[0013] Preferably, in step one, the molar ratio of vinylsilane to 4-bromobenzocyclobutene monomers is 1:1 to 1:2; the molar ratio of the metal catalyst to vinylsilane is 1:1000 to 1:50; the molar ratio of the organophosphine ligand to vinylsilane is 1:1000 to 1:250; the molar ratio of the organic amine to vinylsilane is 1:1 to 1.5:1; the volume molar ratio of the first solvent to vinylsilane is 0.5 to 2.5 L / mol; the reaction temperature of vinylsilane and 4-bromobenzocyclobutene is 70 to 120°C, and the reaction time is 4 to 72 hours; the distillation method includes one or more of atmospheric nitrogen distillation, atmospheric nitrogen rectification, vacuum distillation, and vacuum rectification.

[0014] Preferably, the Meerwein reagent is one or more of trimethoxyonium tetrafluoroborate, triethyloxyonium tetrafluoroborate, tripropyloxyonium tetrafluoroborate, tri-n-butyloxyonium tetrafluoroborate, triisopropyloxyonium tetrafluoroborate, tri-tert-butyloxyonium tetrafluoroborate, trimethyloxyonium hexafluorophosphate, triethyloxyonium hexafluorophosphate, and tripropyloxyonium hexafluorophosphate.

[0015] Preferably, the inorganic base is one or more of potassium carbonate, sodium carbonate, potassium acetate, sodium acetate, sodium bicarbonate, potassium bicarbonate, and ammonium hydroxide; the second solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, toluene, dioxane, and acetonitrile; the third solvent is one or more of dichloromethane, chloroform, chlorobenzene, toluene, and xylene; and the desiccant is one or more of anhydrous sodium sulfate, anhydrous magnesium sulfate, anhydrous calcium chloride, and molecular sieves.

[0016] Preferably, in step two, the molar ratio of benzocyclobutene-vinylsilane to Meerwein reagent is 1:1 to 1:1.5; the molar ratio of benzocyclobutene-vinylsilane to inorganic base is 1:1 to 1:2.0; the volume molar ratio of the second solvent to benzocyclobutene-vinylsilane is 1 to 10 L / mol; the condensation reaction temperature is 60 to 100°C, and the reaction time is 2 to 12 hours; the amount of washing water is 10 to 20 times the mass of benzocyclobutene-vinylsilane; the amount of the third solvent is 5 to 10 times the mass of benzocyclobutene-vinylsilane; the amount of saturated brine is 5 to 10 times the mass of benzocyclobutene-vinylsilane; and the amount of desiccant is 1 to 2 times the mass of benzocyclobutene-vinylsilane.

[0017] The present invention has at least the following beneficial effects: Compared with existing technologies, this method uses readily available and inexpensive raw materials, and the synthesis route can be completed in only two steps. The purification process is also relatively simple, shortening the synthesis time. Furthermore, the product of the first step, benzocyclobutene-vinylsilane, has low viscosity and a significantly lower boiling point compared to the raw materials and catalyst, making it easy to purify and separate. This results in relatively low levels of metal catalyst, phosphine ligands, and halide ions in the product obtained in the second step.

[0018] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached image description: Figure 1 The 1H NMR spectrum of the organosilicon monomer DVS-bis-BCB of benzocyclobutene in Example 1; Figure 2Comparison of the purity of DVS-bis-BCB, an organosilicon monomer of benzocyclobutene, prepared by different methods (ICPMS results). Among them, (Method 1: completed according to the synthesis method of Alan K. Schrock (US Pat. No. 4,812,588); Method 2: completed according to the synthesis method of Robert A. DeVries (US Pat. No. 5,567,835); Patent method: the new method involved in this patent). Detailed implementation method: The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0019] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not imply the presence or addition of one or more other elements or combinations thereof.

[0020] Example 1: (1) The synthetic reaction formula for benzocyclobutene-vinyldimethylethoxysilane is as follows: The specific synthesis process of benzocyclobutene-vinyldimethylethoxysilane is as follows: At room temperature, 183.1 g (1.0 mol) of 4-bromobenzocyclobutene, 195.4 g (1.5 mol) of vinyldimethylethoxysilane, 121.4 g (1.2 mol) of triethylamine, and 1.0 L of acetonitrile were weighed and added to a 2 L round-bottom flask. Under nitrogen protection, 0.67 g (3 mmol) of palladium acetate Pd(OAc)2 and 3.15 g (12 mmol) of triphenylphosphine were added. The mixture was stirred at room temperature for 30 minutes, then heated to 80 °C and stirred for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature. The mixture was first filtered under vacuum, and then the brownish-red filtrate was filtered through coarse silica gel (particle size 1-10 μm). The filtrate was concentrated by rotary evaporation to remove the solvent, and finally distilled under reduced pressure to obtain 194.2 g of colorless liquid, with a yield of 83.6%. (2) The synthesis reaction formula of the organosilicon monomer DVS-bis-BCB of benzocyclobutene is as follows: The specific synthesis process of the benzocyclobutene organosilicon monomer DVS-bis-BCB is as follows: At room temperature, benzocyclobutene-vinyldimethylethoxysilane (174.3 g, 0.75 mol), potassium carbonate (103.65 g, 0.75 mol), and acetonitrile (3.0 L) were weighed and added to a 5 L round-bottom flask. Under nitrogen protection, trimethoxyonium tetrafluoroborate (110.9 g, 0.75 mol) was added. The mixture was stirred at room temperature for 15 minutes, then heated to 100 °C and reacted for 6 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and water (1500 mL) was slowly added while stirring continued. 1000 mL of dichloromethane was added for extraction. The extract was first washed with saturated brine (1000 mL, 250 mL each time, used in 4 portions), then dried with anhydrous sodium sulfate (200 g), and finally filtered and concentrated by rotary evaporation to obtain 275.2 g of a colorless oil, with a yield of 93.9%. The 1H NMR spectrum of the monomer is shown below. Figure 1 As shown, in Figure 2 In the DVS-bis-BCB product, the ICP-MS results showed that elements P, Pd, and Pt were either not detected or had relatively low concentrations.

[0021] Example 2: (1) The synthetic reaction formula for benzocyclobutene-vinyldimethylmethoxysilane is as follows: The specific synthesis process of benzocyclobutene-vinyldimethylmethoxysilane is as follows: At room temperature, 183.1 g (1.0 mol) of 4-bromobenzocyclobutene, 163.8 g (1.5 mol) of vinyldimethylmethoxysilane, 121.4 g (1.2 mol) of triethylamine, and 1.0 L of acetonitrile were weighed and added to a 2 L round-bottom flask. Under nitrogen protection, 0.67 g (3 mmol) of palladium acetate Pd(OAc)2 and 5.07 g (12 mmol) of 1,2-bis(dicyclohexylphospho)-ethane were added. The mixture was stirred at room temperature for 30 minutes, then heated to 75 °C and stirred for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature. The mixture was first filtered under vacuum, and then the brownish-red filtrate was filtered through coarse silica gel (particle size 1-10 μm). The filtrate was concentrated by rotary evaporation to remove the solvent, and finally distilled under reduced pressure to obtain 181.0 g of colorless liquid, with a yield of 82.9%. (2) The synthesis reaction formula of the organosilicon monomer DVS-bis-BCB of benzocyclobutene is as follows: At room temperature, benzocyclobutene-vinyldimethylmethoxysilane (109.2 g, 0.5 mol), potassium carbonate (69.1 g, 0.5 mol), and acetonitrile (2.2 L) were weighed and added to a 5 L round-bottom flask. Under nitrogen protection, trimethoxyonium tetrafluoroborate (73.9 g, 0.5 mol) was added. The mixture was stirred at room temperature for 15 minutes, then heated to 100 °C and reacted for 6 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and water (1000 mL) was slowly added while stirring continued. 1000 mL of dichloromethane was added for extraction. The extract was first washed with saturated brine (1000 mL, 250 mL each time, used 4 times), then dried with anhydrous sodium sulfate (200 g), and finally filtered and concentrated by rotary evaporation to obtain 159.1 g of a colorless oil, with a yield of 81.2%.

[0022] Example 3: (1) The synthetic reaction formula for benzocyclobutene-vinyldimethylethoxysilane is as follows: The specific synthesis process of benzocyclobutene-vinyldimethylethoxysilane is as follows: At room temperature, 183.1 g (1.0 mol) of 4-bromobenzocyclobutene, 195.4 g (1.5 mol) of vinyldimethylethoxysilane, 121.4 g (1.2 mol) of triethylamine, and 1.0 L of acetonitrile were weighed and added to a 2 L round-bottom flask. Under nitrogen protection, 0.67 g (3 mmol) of palladium acetate Pd(OAc)2 and 3.65 g (12 mmol) of tris(o-methylphenyl)phosphine were added. The mixture was stirred at room temperature for 30 minutes, then heated to 80 °C and stirred for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature. The mixture was first filtered under vacuum, and then the brownish-red filtrate was filtered through coarse silica gel (particle size 1-10 μm). The filtrate was concentrated by rotary evaporation to remove the solvent, and finally distilled under reduced pressure to obtain 197.5 g of colorless liquid, with a yield of 85.0%.

[0023] (2) The synthesis reaction formula of the organosilicon monomer DVS-bis-BCB of benzocyclobutene is as follows: The specific synthesis process of the benzocyclobutene organosilicon monomer DVS-bis-BCB is as follows: At room temperature, benzocyclobutene-vinyldimethylethoxysilane (174.3 g, 0.75 mol), potassium carbonate (103.65 g, 0.75 mol), and acetonitrile (3.0 L) were weighed and added to a 5 L round-bottom flask. Under nitrogen protection, triethyloxonium hexafluorophosphate (186.1 g, 0.75 mol) was added. The mixture was stirred at room temperature for 15 minutes, then heated to 100 °C and reacted for 6 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature, and water (1500 mL) was slowly added while stirring continued. 1000 mL of dichloromethane was added for extraction. The extract was first washed with saturated brine (1000 mL, 250 mL each time, used 4 times), then dried with anhydrous sodium sulfate (200 g), and finally filtered and concentrated by rotary evaporation to obtain 179.1 g of a colorless oil, with a yield of 91.7%.

[0024] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. A method for synthesizing a high-purity benzocyclobutene-based organosilicon monomer for semiconductor encapsulation resin, characterized in that, Includes the following steps: Step 1: Using vinylsilane as a raw material, react with 4-bromobenzocyclobutene in the presence of a metal catalyst, an organophosphine ligand, an organic amine, and a first solvent. After the reaction is complete, the mixture is vacuum filtered, filtered with silica gel, concentrated, and distilled to obtain benzocyclobutene-vinylsilane. Step 2: Benzocyclobutene-vinylsilane undergoes a condensation reaction in the presence of Meerwein reagent, inorganic base, and a second solvent. After the reaction is complete, the mixture is filtered, washed with water, extracted with a third solvent, washed with saturated brine, dried with a desiccant, filtered, and concentrated to obtain high-purity benzocyclobutene-based organosilicon monomer DVS-bis-BCB for semiconductor encapsulation resin.

2. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, The vinyl silane is any one of vinyl dimethyl methoxysilane, vinyl dimethyl ethoxysilane, vinyl dimethyl propoxysilane, vinyl dimethyl isopropoxysilane, and vinyl dimethyl tert-butoxysilane.

3. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, The metal catalyst is one or more of palladium chloride, palladium acetate, palladium dichloride of bis(triphenylphosphine)phosphine, palladium tetra(triphenylphosphine)phosphine, palladium dibenzylidene acetone, palladium trifluoroacetate, palladium nitrate, [1,1′-bis(diphenylphosphine)ferrocene]palladium dichloride, and palladium on carbon.

4. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, The organophosphine ligand is one or more of the following: diphenylphosphine, dicyclohexylphosphine, bis(diphenylphosphine)methane, bis(diphenylphosphine)ethane, bis(diphenylphosphine)propane, bis(diphenylphosphine)butane, bis(diphenylphosphine)pentane, bis(diphenylphosphine)benzene, bis(diphenylphosphine)naphthalene, triphenylphosphine, tributylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, tris(o-methylphenyl)phosphine, tris(2-furanyl)phosphine, 1,3,5-triaza-7-phosphaadamantane, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 1,2-bis(dicyclohexylphospho)-ethane, and 1,1'-bis(di-tert-butylphosphine)ferrocene.

5. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, The organic amine is one or more of triethylamine, tri-n-butylamine, isopropyl diethylamine, cyclohexyl diethylamine, tetramethylguanidine, and 1,4-diazabicyclo[2.2.2]octane.

6. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, The first solvent is one or more of toluene, dioxane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.

7. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, In step one, the molar ratio of vinylsilane to 4-bromobenzocyclobutene monomers is 1:1 to 1:2; the molar ratio of the metal catalyst to vinylsilane is 1:1000 to 1:50; the molar ratio of the organophosphine ligand to vinylsilane is 1:1000 to 1:250; the molar ratio of the organic amine to vinylsilane is 1:1 to 1.5:1; the volume molar ratio of the first solvent to vinylsilane is 0.5 to 2.5 L / mol; the reaction temperature of vinylsilane and 4-bromobenzocyclobutene is 70 to 120°C, and the reaction time is 4 to 72 hours; the distillation method includes one or more of atmospheric nitrogen distillation, atmospheric nitrogen rectification, vacuum distillation, and vacuum rectification.

8. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, The Meerwein reagent is one or more of the following: trimethoxyonium tetrafluoroborate, triethyloxyonium tetrafluoroborate, tripropyloxyonium tetrafluoroborate, tri-n-butyloxyonium tetrafluoroborate, triisopropyloxyonium tetrafluoroborate, tri-tert-butyloxyonium tetrafluoroborate, trimethyloxyonium hexafluorophosphate, triethyloxyonium hexafluorophosphate, and tripropyloxyonium hexafluorophosphate.

9. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, The inorganic base is one or more of potassium carbonate, sodium carbonate, potassium acetate, sodium acetate, sodium bicarbonate, potassium bicarbonate, and ammonium hydroxide; the second solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, toluene, dioxane, and acetonitrile; the third solvent is one or more of dichloromethane, chloroform, chlorobenzene, toluene, and xylene; and the desiccant is one or more of anhydrous sodium sulfate, anhydrous magnesium sulfate, anhydrous calcium chloride, and molecular sieve.

10. The method for synthesizing high-purity benzocyclobutene-based organosilicon monomers for semiconductor encapsulation resin as described in claim 1, characterized in that, In step two, the molar ratio of benzocyclobutene-vinylsilane to Meerwein reagent is 1:1 to 1:1.5; the molar ratio of benzocyclobutene-vinylsilane to inorganic base is 1:1 to 1:2.0; the volume molar ratio of the second solvent to benzocyclobutene-vinylsilane is 1 to 10 L / mol; the condensation reaction temperature is 60 to 100°C, and the reaction time is 2 to 12 hours; the amount of washing water used is 10 to 20 times the mass of benzocyclobutene-vinylsilane; the amount of the third solvent used is 5 to 10 times the mass of benzocyclobutene-vinylsilane; the amount of saturated brine used is 5 to 10 times the mass of benzocyclobutene-vinylsilane; and the amount of desiccant used is 1 to 2 times the mass of benzocyclobutene-vinylsilane.

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