Preparation of thermally cured benzocyclobutene-based mq silicone resins and their use in the production of glass fiber composites

Abstract

The application discloses a preparation of a thermosetting benzocyclobutene-based MQ silicone resin and application thereof in preparing a glass fiber composite material, and comprises the following steps: stirring and reacting an organic silicon source, a solvent, a catalyst and water at 30-50 DEG C for 30-90 min to form a mixed solution A; uniformly mixing divinylsiloxane-benzocyclobutene and the solvent to form a mixed solution B, adding the mixed solution B into the mixed solution A, and heating to 65-80 DEG C for 1-3 h; adding an organic phase after the reaction is completed, washing with water for several times until neutral, removing the solvent by vacuum distillation, and vacuum drying; and obtaining the thermosetting benzocyclobutene-based MQ silicone resin. The thermosetting benzocyclobutene-based MQ silicone resin has excellent dielectric properties, mechanical properties, heat resistance and chemical stability, and the cured resin formed by thermal crosslinking has the properties of low dielectric, high tensile strength, high bending strength, chemical stability and heat resistance.

Description

Technical Field

[0001] This invention relates to the field of MQ silicone resin technology, specifically to the preparation of a thermosetting benzocyclobutene-based MQ silicone resin and its application in the preparation of glass fiber composite materials. Background Technology

[0002] MQ silicone resin is composed of monofunctional structural units (R3SiO2). 1 / 2 ) and four functional structural units (R3SiO) 4 / 2 MQ silicone resin is a covalently bonded silicone resin. As a novel organosilicon polymer material, MQ silicone resin is widely used as a reinforcing filler in liquid silicone rubber, a reinforcing agent in LED encapsulation materials, an adhesive tackifier, an electrical insulating layer, and an organosilicon pressure-sensitive adhesive. Introducing different organic groups into MQ silicone resin is an important way to obtain MQ silicone resin with superior performance and better reinforcing effect; introducing different organic groups is an important way to change the performance of silicone resin from a structural perspective, and by controlling the types of organic groups, MQ silicone resins with different performance requirements can be obtained.

[0003] Currently, traditional MQ silicone resins are classified into three types: methyl, vinyl, and phenyl. When used as reinforcing agents, these three types require pretreatment to better form chemical bonds with the matrix material for cross-linking. During the cross-linking process, other small molecule substances such as silane coupling agents, initiators, and vulcanizing agents also need to be added. Therefore, incomplete removal of small molecule substances during subsequent purification will have a certain impact on its performance and make the process more complicated.

[0004] According to existing reports (US Pat. 5882836, 1999), tetradivinylsiloxane-bisbenzocyclobutene (DVS-BCB) can be photocured / thermally cured and can be used as passivation films, photoresists, insulating layers in the manufacture of electrical devices, protective films for semiconductor elements, and interlayer dielectrics in multi-chip modules and other multilayer electronic circuits. The ring-opening polymerization of benzocyclobutene monomers does not require the addition of catalysts and initiators, and does not generate small molecule byproducts during the reaction.

[0005] Therefore, by introducing organic groups with thermally open four-membered rings and double bonds, thermosetting benzocyclobutene-based MQ silicone resins with superior performance, simpler crosslinking, better reinforcement effect, and wider applicability can be obtained.

[0006] In the application of electrical insulation materials, there are not only technical requirements for their strength, toughness, chemical stability, and temperature resistance, but also for their dielectric constant. The composite of glass fiber and traditional MQ silicone resin has shortcomings in terms of manufacturing process and performance. Summary of the Invention

[0007] This invention prepares MQ silicone resins of different molecular weights by adjusting tetradivinylsiloxane-bisbenzocyclobutene (DVS-BCB) as the M unit and methyl orthosilicate / ethyl orthosilicate as the Q unit in different ratios under different hydrolysis and condensation conditions to meet the technical requirements of different technical fields. Furthermore, it prepares composite materials with glass fibers that have low dielectric constant, high tensile strength, high flexural strength, high mechanical stability, and high thermal stability.

[0008] This invention relates to the preparation of a thermosetting benzocyclobutene-based MQ silicone resin and its application in the preparation of glass fiber composite materials. On the one hand, it addresses the current lack of use of the tetra-divinylsiloxane-bisbenzocyclobutene (DVS-BCB) organic group and its synthesis method in traditional MQ silicone resins; on the other hand, it fills the gap in the scarcity of thermosetting benzocyclobutene-based MQ silicone resins in the domestic market; and on the other hand, it produces thermosetting benzocyclobutene-based MQ silicone resin-glass fiber composite materials with low dielectric constant, high strength, and excellent temperature resistance.

[0009] 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.

[0010] To achieve these objectives and other advantages according to the present invention, a method for preparing a thermosetting benzocyclobutene-based MQ silicone resin is provided, comprising the following steps:

[0011] Step 1: Stir the organosilicon source, solvent, catalyst and water at 30~50℃ for 30~90min to form mixture A;

[0012] Step 2: Mix divinylsiloxane-bisbenzocyclobutene and solvent evenly to form mixture B. Add mixture B to mixture A and heat to 65~80℃ to react for 1~3 hours.

[0013] Step 3: After the reaction is complete, add the organic phase for extraction and wash with water several times until neutral. Remove the solvent by vacuum distillation and vacuum dry to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0014] Preferably, the thermosetting benzocyclobutenyl MQ silicone resin prepared in step three is hydrolyzed and condensed again with M units of other different R groups to remove unreacted alkoxy or silanol groups, thereby obtaining thermosetting benzocyclobutenyl MQ silicone resin.

[0015] Preferably, the thermosetting benzocyclobutene-based MQ silicone resin has the following structural formula:

[0016] Where x = 0~50, y = 0~50, z = 0~50; R is one of vinyl, alkyl, phenyl, vinylbenzocyclobutenyl or silanealkyl.

[0017] Preferably, the solvents used in steps one and two are all polar, weakly polar, or non-polar solvents; and the organosilicon source is methyl orthosilicate or ethyl orthosilicate.

[0018] Preferably, the solvents in steps one and two are all selected from ethanol, toluene, n-hexane, ethanol, isopropanol, or tetrahydrofuran; and the catalyst is one or a combination of concentrated hydrochloric acid, concentrated sulfuric acid, glacial acetic acid, or fluorinated acids.

[0019] Preferably, the mass ratio of the organosilicon source to divinylsiloxane-bisbenzocyclobutene is 1.5~3.5:1; the amount of solvent in the mixture A is 10%~50% of the mass of the organosilicon source; the amount of water is 10~35% of the total mass of the organosilicon source and divinylsiloxane-bisbenzocyclobutene; and the amount of catalyst added is 10% of the total mass of the organosilicon source and divinylsiloxane-bisbenzocyclobutene. -3 ~5×10 -2 The amount of solvent used in mixture B is 10% to 50% of the mass of divinylsiloxane-bisbenzocyclobutene.

[0020] Preferably, the extractant used in the organic phase extraction is any one of ethyl acetate, toluene, and dichloromethane.

[0021] Preferably, thermosetting benzocyclobutenyl MQ silicone resin and toluene are added to a reactor along with ultrapure water, concentrated hydrochloric acid catalyst, and a capping agent. The mixture is reacted at a constant temperature of 60-80°C for 1-3 hours. After the mixture cools to room temperature, it is washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out. The organic phase is concentrated by rotary evaporation and vacuum dried to obtain thermosetting benzocyclobutenyl MQ silicone resin that has been further hydrolyzed and condensed to remove unreacted alkoxy or silanol groups. The capping agent is any one of hexamethyldisiloxane, tetramethyldivinyldisiloxane, 4-(ethoxyvinyldimethylsilyl)benzocyclobutene, tetramethyldiphenyldisiloxane, and tetramethyldihydrodisiloxane.

[0022] The present invention also provides an application of the thermosetting benzocyclobutene MQ silicone resin prepared by the preparation method described above in the preparation of glass fiber composite materials. The thermosetting benzocyclobutene MQ silicone resin and a diluent are mixed to obtain a resin mixture, and glass fibers are impregnated in the mixture and thermosetting is performed to obtain a glass fiber composite material.

[0023] Preferably, based on the total mass of the glass fiber composite material as 100%, the content of the mixed adhesive is 25-50%, and the content of the glass fiber is 50-75%; the glass fiber is any one of short glass fiber, continuous glass fiber, and glass fiber mat.

[0024] The present invention has at least the following beneficial effects:

[0025] (1) The preparation method of this invention is simple, produces no by-products, and has high atom utilization. The process is mature, uses few types of solvents, has low product recovery difficulty, and a high recovery rate. The reaction of this invention is carried out at 30-80℃, with mild conditions and low energy consumption. This invention has few factors affecting the molecular weight of the product, and the molecular weight is easy to control. By adjusting the molar ratio of the M unit of divinylsiloxane-bisbenzocyclobutene (DVS-BCB) to the Q unit of tetraethyl orthosilicate (methyl orthosilicate), the preparation of MQ silicone resins with different molecular weights and the control of molecular weight can be achieved. The system of this invention produces few reaction by-products, has a short production cycle, high efficiency, and is fully industrializable. The product of this invention is completely soluble in polar or weakly polar solvents.

[0026] (2) The thermosetting benzocyclobutene-based MQ silicone resin described in this invention forms a cured resin with superior dielectric properties, mechanical properties, heat resistance and chemical stability through thermal crosslinking. It can then be combined with glass fiber to prepare a composite material with low dielectric, high tensile strength, high flexural strength, chemical stability and heat resistance.

[0027] 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 Figure Description

[0028] Figure 1 The infrared FTIR spectrum of the thermosetting benzocyclobutene-based MQ silicone resin prepared in Example 5;

[0029] Figure 2 The 1H NMR spectrum of the thermosetting benzocyclobutene-based MQ silicone resin prepared in Example 5;

[0030] Figure 3 Thermogravimetric curve of the thermosetting benzocyclobutene-based MQ silicone resin prepared in Example 5 after thermosetting;

[0031] Figure 4 The dielectric constant curve of the thermosetting benzocyclobutene-based MQ silicone resin prepared in Example 5 after thermosetting. Detailed Implementation

[0032] 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.

[0033] 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.

[0034] Example 1:

[0035] In a 50 mL reaction flask, tetraethyl orthosilicate (13.27 g, 63.8 mmol), ultrapure water (2.53 g, 140.3 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) was added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0036] Example 2:

[0037] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (1.61 g, 89.3 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0038] Example 3:

[0039] In a 50 mL reaction flask, tetraethyl orthosilicate (6.63 g, 31.9 mmol), ultrapure water (1.38 g, 76.5 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) was added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0040] Example 4:

[0041] In a 50 mL reaction flask, tetraethyl orthosilicate (5.31 g, 25.5 mmol), ultrapure water (1.15 g, 63.8 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0042] Example 5:

[0043] In a 50 mL reaction flask, tetraethyl orthosilicate (4.43 g, 21.3 mmol), ultrapure water (1.15 g, 63.8 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, the organic phase is concentrated by rotary evaporation, and finally dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene MQ silicone resin.

[0044] Figure 1 The infrared FTIR spectrum of the thermosetting benzocyclobutene-based MQ silicone resin prepared in Example 5 is shown. The molecular structure was determined by the vibrational peaks of the molecular absorption groups; the stretching vibration peaks representing the methyl group and the methylene group attached to silicon are located at 2958 cm⁻¹. -1 and 2839 cm -1 Location. At 1605 cm -1 and 1578 cm -1 The peak at 1088 cm⁻¹ is caused by the C=C tensile vibration of the BCB six-membered ring. -1 The strong peak at 1254 cm⁻¹ is generated by the stretching vibrations of Si-O-Si and Si-O-CH₃. -1 and 1419 cm -1 The peaks at 802 cm⁻¹ are composed of as(CH) and s(CH) groups of Si-CH₃, respectively. -1 The absorption band at 987 cm⁻¹ is due to the stretching vibration of Si-C. -1 and 844 cm -1 The absorption band at 691 cm⁻¹ is the bending vibration peak of CH in CH=CH bonded to Si. The out-of-plane bending absorption band of CH is located at 691 cm⁻¹. -1 Place.

[0045] Figure 2The 1H NMR spectrum of the thermosetting benzocyclobutenyl MQ silicone resin prepared in Example 5 is shown below. The chemical shifts of hydrogen atoms in the benzene ring are above 6.9 ppm; the chemical shifts of hydrogen atoms in the vinyl group are above 5.6 ppm; the chemical shifts of hydrogen atoms on the benzo four-membered ring are around 3.2 ppm; and the chemical shifts of hydrogen atoms in the methyl group attached to the silicon-oxygen-silicon bond are around 0.2~0.3 ppm.

[0046] Example 6:

[0047] In a 50 mL reaction flask, tetraethyl orthosilicate (3.79 g, 18.2 mmol), ultrapure water (0.88 g, 49.2 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0048] Example 7:

[0049] In a 50 mL reaction flask, tetraethyl orthosilicate (3.32 g, 15.9 mmol), ultrapure water (0.80 g, 44.6 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0050] Example 8:

[0051] In a 50 mL reaction flask, tetraethyl orthosilicate (2.95 g, 14.2 mmol), ultrapure water (0.74 g, 41.1 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0052] Example 9:

[0053] In a 50 mL reaction flask, tetraethyl orthosilicate (2.65 g, 12.7 mmol), ultrapure water (0.69 g, 38.3 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0054] Example 10:

[0055] In a 50 mL reaction flask, tetraethyl orthosilicate (2.41 g, 11.6 mmol), ultrapure water (0.65 g, 36 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0056] Example 11:

[0057] In a 50 mL reaction flask, tetraethyl orthosilicate (2.21 g, 10.6 mmol), ultrapure water (0.61 g, 34 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0058] Example 12:

[0059] In a 50 mL reaction flask, tetraethyl orthosilicate (2.04 g, 9.8 mmol), ultrapure water (0.58 g, 32.4 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0060] Example 13:

[0061] In a 50 mL reaction flask, tetraethyl orthosilicate (1.89 g, 9.1 mmol), ultrapure water (0.56 g, 31 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0062] Example 14:

[0063] In a 50 mL reaction flask, tetraethyl orthosilicate (1.77 g, 8.5 mmol), ultrapure water (0.53 g, 29.7 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0064] Example 15:

[0065] In a 50 mL reaction flask, tetraethyl orthosilicate (1.65 g, 7.9 mmol), ultrapure water (0.51 g, 28.7 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0066] Example 16:

[0067] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (1.61 g, 89.3 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (2 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 2 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0068] Example 17:

[0069] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (1.61 g, 89.3 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (0.5 wt%, meaning the amount of concentrated hydrochloric acid catalyst is 0.5 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0070] Example 18:

[0071] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (1.61 g, 89.3 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (3 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 3 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0072] Example 19:

[0073] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (1.61 g, 89.3 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (3 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 3 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0074] Example 20:

[0075] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (1.95 g, 108.5 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0076] Example 21:

[0077] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (2.29 g, 128 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0078] Example 22:

[0079] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (2.64 g, 146.7 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetrahydrofuran used), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) was added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0080] Example 23:

[0081] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (2.98 g, 165.8 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0082] Example 24:

[0083] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (2.98 g, 165.8 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0084] 0.5 g of thermosetting benzocyclobutenyl MQ silicone resin and toluene (20 wt%, where toluene is 20 wt% of the amount of thermosetting benzocyclobutenyl MQ silicone resin) were added to a 50 mL reaction flask. Ultrapure water (0.1 g, 5.5 mmol), concentrated hydrochloric acid catalyst (1 wt%, where concentrated hydrochloric acid is 1 wt% of the total mass of the thermosetting benzocyclobutenyl MQ silicone resin and hexamethyldisiloxane), and hexamethyldisiloxane (0.2 g, 1 mmol) were added. The mixture was reacted at 70 °C for 2 h. After the mixture cooled to room temperature, it was washed several times with ultrapure water to remove residual catalyst. The organic phase was then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate was filtered off. The organic phase was concentrated by rotary evaporation and finally dried in a vacuum oven at 100 °C for 8 h to obtain a thermosetting benzocyclobutenyl MQ silicone resin that had undergone further hydrolysis and condensation to remove unreacted silanol groups and siloxanes.

[0085] Example 25:

[0086] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (2.98 g, 165.8 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0087] 0.5 g of thermosetting benzocyclobutenyl MQ silicone resin and toluene (20 wt%, where toluene is 20 wt% of the amount of thermosetting benzocyclobutenyl MQ silicone resin) were added to a 50 mL reaction flask. Ultrapure water (0.1 g, 5.5 mmol), concentrated hydrochloric acid catalyst (1 wt%, where concentrated hydrochloric acid is 1 wt% of the total mass of the thermosetting benzocyclobutenyl MQ silicone resin and hexamethyldisiloxane), and hexamethyldisiloxane end-capping agent (0.2 g, 1 mmol) were added. The mixture was reacted at 70 °C for 2 h. After cooling to room temperature, the mixture was washed several times with ultrapure water to remove residual catalyst. The organic phase was then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate was filtered off. The organic phase was concentrated by rotary evaporation and finally dried in a vacuum oven at 100 °C for 8 h to obtain a thermosetting benzocyclobutenyl MQ silicone resin that had undergone further hydrolysis and condensation to remove unreacted silanol groups and siloxanes.

[0088] Example 26:

[0089] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (2.98 g, 165.8 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene capping agent (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0090] 0.5 g of thermosetting benzocyclobutenyl MQ silicone resin and toluene (20 wt%, where toluene is 20 wt% of the amount of thermosetting benzocyclobutenyl MQ silicone resin) were added to a 50 mL reaction flask. Ultrapure water (0.1 g, 5.5 mmol), concentrated hydrochloric acid catalyst (1 wt%, where concentrated hydrochloric acid is 1 wt% of the total mass of the thermosetting benzocyclobutenyl MQ silicone resin and hexamethyldisiloxane), and end-capping agent tetramethyldisiloxane (0.13 g, 1 mmol) were added. The mixture was reacted at 70 °C for 2 h. After cooling to room temperature, the mixture was washed several times with ultrapure water to remove residual catalyst. The organic phase was then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate was filtered off. The organic phase was concentrated by rotary evaporation and finally dried in a vacuum oven at 100 °C for 8 h to obtain a thermosetting benzocyclobutenyl MQ silicone resin that had undergone further hydrolysis and condensation to remove unreacted silanol groups and siloxanes.

[0091] Example 27:

[0092] In a 50 mL reaction flask, tetraethyl orthosilicate (7.96 g, 38.3 mmol), ultrapure water (2.98 g, 165.8 mmol), tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of tetraethyl orthosilicate), and concentrated hydrochloric acid catalyst (1 wt%, meaning the amount of concentrated hydrochloric acid catalyst used is 1 wt% of the amount of tetraethyl orthosilicate and divinylsiloxane-bisbenzocyclobutene (DVS-BCB)) were added and reacted at 50 °C for 1 h. Then, tetrahydrofuran (10 wt%, meaning the amount of tetrahydrofuran used is 10 wt% of the amount of divinylsiloxane-bisbenzocyclobutene) and divinylsiloxane-bisbenzocyclobutene (DVS-BCB) (5 g, 12.7 mmol) were added and the temperature was raised to 75 °C and reacted at 75 °C for 2 h. After the mixture is cooled to room temperature, an organic phase is added for extraction and washed several times with ultrapure water to remove residual catalyst. The organic phase is then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate is filtered out, and the organic phase is concentrated by rotary evaporation. Finally, it is dried in a vacuum oven at 100°C for 8 hours to obtain thermosetting benzocyclobutene-based MQ silicone resin.

[0093] 0.5 g of thermosetting benzocyclobutenyl MQ silicone resin and toluene (20 wt%, where toluene is 20 wt% of the amount of thermosetting benzocyclobutenyl MQ silicone resin) were added to a 50 mL reaction flask. Ultrapure water (0.1 g, 5.5 mmol), concentrated hydrochloric acid catalyst (1 wt%, where concentrated hydrochloric acid is 1 wt% of the total mass of the thermosetting benzocyclobutenyl MQ silicone resin and hexamethyldisiloxane), and end-capping agent dimethylphenylethoxysiloxane (0.18 g, 1 mmol) were added. The mixture was reacted at 70 °C for 2 h. After cooling to room temperature, the mixture was washed several times with ultrapure water to remove residual catalyst. The organic phase was then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate was filtered off. The organic phase was concentrated by rotary evaporation and finally dried in a vacuum oven at 100 °C for 8 h to obtain a thermosetting benzocyclobutenyl MQ silicone resin that had undergone further hydrolysis and condensation to remove unreacted silanol groups and siloxanes.

[0094] Example 28:

[0095] Using an electronic balance, 10g of the thermosetting benzocyclobutene MQ silicone resin prepared in Example 5 was weighed and mixed evenly with a diluent (80% of the mass of the thermosetting benzocyclobutene MQ silicone resin) to form a paste. The release agent was sprayed onto the steel plate and mold. After spraying, the mixture was allowed to stand for 15 minutes. This process was repeated three times. Then, 30g of chopped glass fibers were weighed and spread evenly on the steel plate coated with the release agent. Next, a glass rod was used to guide and impregnate the fiber fabric with the paste formed by the thermosetting benzocyclobutene MQ silicone resin and diluent, ensuring the resin evenly covered the fibers to obtain a glass fiber prepreg. Finally, the prepreg was left at room temperature for 30 minutes. The mold was placed in an oven and preheated to 180°C. After preheating, the steel plate with the glass fiber prepreg was placed into the mold, and another steel plate of the same size was placed on top of the glass fiber prepreg. The mold was then closed and gently pressed to ensure the two ends fit together. The mold was placed in a hot press. First, without applying pressure, the composite laminate was heated from room temperature (25°C) to 180°C at a heating rate of 2°C / min. After reaching the desired temperature, a pressure of 0.1 MPa was applied to the mold, and once the pressure reached the predetermined value, both temperature and pressure were maintained for 1.5 hours. To ensure complete resin curing, the mold was then heated to 250°C at a rate of 2°C / min and held at that temperature for another 2 hours. Finally, the mold was gradually cooled to room temperature at a cooling rate of 2.5°C / min. The tensile and flexural properties of the composite material were tested, showing a tensile strength of 30 MPa and a flexural strength of 80 MPa.

[0096] Example 29:

[0097] 10g of the thermosetting benzocyclobutene MQ silicone resin prepared in Example 5 was weighed using an electronic balance and mixed evenly with a diluent (80% of the mass of the thermosetting benzocyclobutene MQ silicone resin) to form a paste. The release agent was sprayed onto the steel plate and the mold. After spraying, the mixture was allowed to stand for 15 minutes. This process was repeated three times. Then, 23.34g of chopped glass fibers were weighed and spread evenly on the steel plate coated with the release agent. Next, a glass rod was used to guide and impregnate the fiber fabric with the paste formed by the thermosetting benzocyclobutene MQ silicone resin and diluent, ensuring the resin evenly covered the fibers to obtain a glass fiber prepreg. Finally, the prepreg was left at room temperature for 30 minutes. The mold was placed in an oven and preheated to 180°C. After preheating, the steel plate with the glass fiber prepreg was placed into the mold, and another steel plate of the same size was placed on top of the glass fiber prepreg. The mold was then closed and gently pressed to ensure the two ends of the mold were in contact. The mold was placed in a hot press. First, without applying pressure, the composite laminate was heated from room temperature (25°C) to 180°C at a heating rate of 2°C / min. After reaching the desired temperature, a pressure of 0.1 MPa was applied to the mold, and once the predetermined pressure was reached, both temperature and pressure were maintained for 1.5 hours. To ensure complete resin curing, the mold was then heated to 250°C at a rate of 2°C / min and held at this temperature for another 2 hours. Finally, the mold was gradually cooled to room temperature at a cooling rate of 2.5°C / min. The tensile and flexural properties of the composite material were tested, showing a tensile strength of 40 MPa and a flexural strength of 95 MPa.

[0098] Example 30:

[0099] 10g of the thermosetting benzocyclobutene MQ silicone resin prepared in Example 5 was weighed using an electronic balance and mixed evenly with a diluent (80% of the mass of the thermosetting benzocyclobutene MQ silicone resin) to form a paste. The release agent was sprayed onto the steel plate and mold, and allowed to stand for 15 minutes after spraying. This process was repeated three times. Then, 18.58g of chopped glass fibers were weighed and spread evenly on the steel plate coated with the release agent. Next, a glass rod was used to guide and impregnate the fiber fabric with the paste formed by the thermosetting benzocyclobutene MQ silicone resin and diluent, ensuring the resin evenly covered the fibers to obtain a glass fiber prepreg. Finally, the prepreg was left at room temperature for 30 minutes. The mold was placed in an oven and preheated to 180°C. After preheating, the steel plate with the glass fiber prepreg was placed into the mold, and another steel plate of the same size was placed on top of the glass fiber prepreg. The mold was then closed and gently pressed to ensure the two ends of the mold were in contact. The mold was placed in a hot press. First, without applying pressure, the composite laminate was heated from room temperature (25°C) to 180°C at a heating rate of 2°C / min. After reaching the desired temperature, a pressure of 0.1 MPa was applied to the mold, and once the pressure reached the predetermined value, both temperature and pressure were maintained for 1.5 hours. To ensure complete resin curing, the mold was then heated to 250°C at a rate of 2°C / min and held at that temperature for another 2 hours. Finally, the mold was gradually cooled to room temperature at a cooling rate of 2.5°C / min. The tensile and flexural properties of the composite material were tested, showing a tensile strength of 45 MPa and a flexural strength of 110 MPa.

[0100] Example 31:

[0101] Using an electronic balance, 10g of the thermosetting benzocyclobutene MQ silicone resin prepared in Example 5 was weighed and mixed evenly with a diluent (80% of the mass of the thermosetting benzocyclobutene MQ silicone resin) to form a paste. The release agent was sprayed onto the steel plate and mold. After spraying, the mixture was allowed to stand for 15 minutes. This process was repeated three times. Then, 15g of chopped glass fibers were weighed and spread evenly on the steel plate coated with the release agent. Next, a glass rod was used to guide and impregnate the fiber fabric with the paste formed by the thermosetting benzocyclobutene MQ silicone resin and diluent, ensuring the resin evenly covered the fibers to obtain a glass fiber prepreg. Finally, the prepreg was left at room temperature for 30 minutes. The mold was placed in an oven and preheated to 180°C. After preheating, the steel plate with the glass fiber prepreg was placed into the mold, and another steel plate of the same size was placed on top of the glass fiber prepreg. The mold was then closed and gently pressed to ensure the two ends of the mold were in contact. The mold was placed in a hot press. First, without applying pressure, the composite laminate was heated from room temperature (25°C) to 180°C at a heating rate of 2°C / min. After reaching the desired temperature, a pressure of 0.1 MPa was applied to the mold, and once the pressure reached the predetermined value, both temperature and pressure were maintained for 1.5 hours. To ensure complete resin curing, the mold was then heated to 250°C at a rate of 2°C / min and held at this temperature for another 2 hours. Finally, the mold was gradually cooled to room temperature at a cooling rate of 2.5°C / min. The tensile and flexural properties of the composite material were tested, showing a tensile strength of 25 MPa and a flexural strength of 70 MPa.

[0102] Example 32:

[0103] Using an electronic balance, 10g of the thermosetting benzocyclobutene MQ silicone resin prepared in Example 5 was weighed and mixed evenly with a diluent (80% of the mass of the thermosetting benzocyclobutene MQ silicone resin) to form a paste. The release agent was sprayed onto the steel plate and the mold. After spraying, the mixture was allowed to stand for 15 minutes. This process was repeated three times. Then, 12.22g of chopped glass fibers were weighed and spread evenly on the steel plate coated with the release agent. Next, a glass rod was used to guide and impregnate the fiber fabric with the paste formed by the thermosetting benzocyclobutene MQ silicone resin and diluent, ensuring the resin evenly covered the fibers to obtain a glass fiber prepreg. Finally, the prepreg was left at room temperature for 30 minutes. The mold was placed in an oven and preheated to 180°C. After preheating, the steel plate with the glass fiber prepreg was placed into the mold, and another steel plate of the same size was placed on top of the glass fiber prepreg. The mold was then closed and gently pressed to ensure the two ends of the mold were in contact. The mold was placed in a hot press. First, without applying pressure, the composite laminate was heated from room temperature (25°C) to 180°C at a heating rate of 2°C / min. After reaching the desired temperature, a pressure of 0.1 MPa was applied to the mold, and once the pressure reached the predetermined value, both temperature and pressure were maintained for 1.5 hours. To ensure complete resin curing, the mold was then heated to 250°C at a rate of 2°C / min and held at that temperature for another 2 hours. Finally, the mold was gradually cooled to room temperature at a cooling rate of 2.5°C / min. The tensile and flexural properties of the composite material were tested, showing a tensile strength of 35 MPa and a flexural strength of 85 MPa.

[0104] Example 33:

[0105] Using an electronic balance, 10g of the thermosetting benzocyclobutene MQ silicone resin prepared in Example 5 was weighed and mixed evenly with a diluent (80% of the mass of the thermosetting benzocyclobutene MQ silicone resin) to form a paste. The release agent was sprayed onto the steel plate and mold. After spraying, the mixture was allowed to stand for 15 minutes. This process was repeated three times. Then, 10g of chopped glass fibers were weighed and spread evenly on the steel plate coated with the release agent. Next, a glass rod was used to guide and impregnate the fiber fabric with the paste formed by the thermosetting benzocyclobutene MQ silicone resin and diluent, ensuring the resin evenly covered the fibers to obtain a glass fiber prepreg. Finally, the prepreg was left at room temperature for 30 minutes. The mold was placed in an oven and preheated to 180°C. After preheating, the steel plate with the glass fiber prepreg was placed into the mold, and another steel plate of the same size was placed on top of the glass fiber prepreg. The mold was then closed and gently pressed to ensure the two ends of the mold were in contact. The mold was placed in a hot press. First, without applying pressure, the composite laminate was heated from room temperature (25°C) to 180°C at a heating rate of 2°C / min. After reaching the desired temperature, a pressure of 0.1 MPa was applied to the mold, and once the pressure reached the predetermined value, both temperature and pressure were maintained for 1.5 hours. To ensure complete resin curing, the mold was then heated to 250°C at a rate of 2°C / min and held at that temperature for another 2 hours. Finally, the mold was gradually cooled to room temperature at a cooling rate of 2.5°C / min. The tensile and flexural properties of the composite material were tested, and the tensile strength was 50 MPa and the flexural strength was 100 MPa.

[0106] Example 34:

[0107] Weigh 0.5g of the thermosetting benzocyclobutene-based MQ silicone resin prepared in Example 5 and place it in a glass tube with a diameter of 3mm. Place the tube in a vacuum thermosetting chamber for a programmed temperature rise process. The temperature rise process is as follows: 160℃ for 1h, 180℃ for 1h, 200℃ for 2h, 215℃ for 2h, 230℃ for 2h, 215℃ for 1h, 200℃ for 1h, 180℃ for 1h, 160℃ for 1h, and then allow it to cool naturally to obtain a cured cylindrical resin with a high crosslinking density.

[0108] Figure 3 The thermogravimetric curve of the thermosetting benzocyclobutene-based MQ silicone resin prepared in Example 5 after thermosetting shows that the decomposition temperature of the thermosetting polymer at 5% weight loss (T5%) is above 450℃, indicating high thermal stability.

[0109] Figure 4 The dielectric constant curve of the thermosetting benzocyclobutene-based MQ silicone resin prepared in Example 5 is shown; it can be seen that the dielectric constant of the thermosetting polymer at 10MHz is 2.75.

[0110] In Examples 1-27 above, the catalyst can be replaced with concentrated sulfuric acid, glacial acetic acid, or fluorinated acid, and tetraethyl orthosilicate can be replaced with methyl orthosilicate.

[0111] In Examples 25-27 above, the capping agent can be replaced with an alkoxysilane compound containing alkyl, phenyl, vinyl, silane, benzocyclobutene, or other similar groups.

[0112] The reaction mechanism of this invention is as follows:

[0113] Tetraethyl orthosilicate (methyl orthosilicate) hydrolyzes under acidic conditions to form silanol groups, which then condense to form polymers of a certain molecular weight. Divinylsiloxane-bisbenzocyclobutene (DVS-BCB) hydrolyzes under acidic conditions to form silanol groups, which then condense with the silanol groups or siloxanes produced by tetraethyl orthosilicate to introduce organic groups, thereby forming branched benzocyclobutene MQ silicone resin with a certain molecular weight. By adjusting the molar ratio of divinylsiloxane-bisbenzocyclobutene (DVS-BCB) to tetraethyl orthosilicate (methyl orthosilicate), the catalyst content, the amount of water, and the temperature, the molecular weight and degree of condensation can be changed, resulting in excellent MQ silicone resins.

[0114] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. The invention can be applied to various fields suitable for it, and further modifications can be readily implemented by those skilled in the art. 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 preparing a thermosetting benzocyclobutene-based MQ silicone resin, characterized in that, Includes the following steps: Step 1: Stir the organosilicon source, solvent, catalyst and water at 30~50℃ for 30~90min to form mixture A; Step 2: Mix divinylsiloxane-bisbenzocyclobutene and solvent to form a mixture B. Add mixture B to mixture A and heat to 65~80℃ for 1~3 hours. Step 3: After the reaction is complete, add the organic phase for extraction and wash with water several times until neutral. Remove the solvent by vacuum distillation and vacuum dry to obtain thermosetting benzocyclobutene-based MQ silicone resin. The organosilicon source is methyl orthosilicate or ethyl orthosilicate; The mass ratio of the organosilicon source to divinylsiloxane-bisbenzocyclobutene is 0.886:1; the amount of solvent in mixture A is 10%~50% of the mass of the organosilicon source; the amount of water is 10~35% of the total mass of the organosilicon source and divinylsiloxane-bisbenzocyclobutene; and the amount of catalyst added is 10% of the total mass of the organosilicon source and divinylsiloxane-bisbenzocyclobutene. -3 ~5×10 -2 The amount of solvent used in mixture B is 10% to 50% of the mass of divinylsiloxane-bisbenzocyclobutene.

2. The method for preparing thermosetting benzocyclobutene-based MQ silicone resin as described in claim 1, characterized in that, The solvents used in steps one and two are all polar, weakly polar, or non-polar solvents.

3. The method for preparing thermosetting benzocyclobutene-based MQ silicone resin as described in claim 1, characterized in that, The solvents used in steps one and two are all selected from ethanol, toluene, n-hexane, isopropanol, or tetrahydrofuran; the catalyst is one or a combination of concentrated hydrochloric acid, concentrated sulfuric acid, glacial acetic acid, or fluorinated acids.

4. The method for preparing thermosetting benzocyclobutene-based MQ silicone resin as described in claim 1, characterized in that, The organic phase extraction uses any one of ethyl acetate, toluene, or dichloromethane as the extractant.

5. The method for preparing thermosetting benzocyclobutene-based MQ silicone resin as described in claim 1, characterized in that, Thermosetting benzocyclobutenyl MQ silicone resin and toluene were added to a reactor along with ultrapure water, concentrated hydrochloric acid catalyst, and a capping agent. The mixture was reacted at a constant temperature of 60-80°C for 1-3 hours. After the mixture cooled to room temperature, it was washed several times with ultrapure water to remove residual catalyst. The organic phase was then dried with anhydrous sodium sulfate. After several hours, the sodium sulfate was filtered out. The organic phase was concentrated by rotary evaporation and vacuum dried to obtain thermosetting benzocyclobutenyl MQ silicone resin that had been further hydrolyzed and condensed to remove unreacted alkoxy or silanol groups. The capping agent was any one of hexamethyldisiloxane, tetramethyldivinyldisiloxane, 4-(ethoxyvinyldimethylsilyl)benzocyclobutene, tetramethyldiphenyldisiloxane, and tetramethyldihydrodisiloxane.

6. The application of a thermosetting benzocyclobutene-based MQ silicone resin prepared by the preparation method according to any one of claims 1 to 5 in the preparation of glass fiber composite materials, characterized in that, A thermosetting benzocyclobutene-based MQ silicone resin and a diluent are mixed to obtain a resin mixture. Glass fibers are then impregnated in the mixture and thermosetting is performed to obtain a glass fiber composite material.

7. The application as described in claim 6, characterized in that, Based on the total mass of the glass fiber composite material as 100%, the content of the mixed adhesive is 25-50%, and the content of the glass fiber is 50-75%; the glass fiber is any one of short glass fiber, continuous glass fiber, and glass fiber mat.

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