Silicone resin composition, method for producing the same, and use thereof

Abstract

The application provides a silicone resin composition and a preparation method and application thereof, and relates to the technical field of new silicone material preparation. The preparation raw material of the silicone resin composition comprises 70-90 parts of methyl trialkoxysilane, 1-10 parts of vinyl trialkoxysilane, 1.5-15 parts of trialkoxy hydrogen silane, 3-15 parts of 3-glycidyl ether oxypropyl trimethoxysilane, 5-20 parts of n-butyl titanate, 30-50 parts of a compatilizer, 40-70 parts of deionized water, 3-10 parts of a catalyst, 0.02-0.7 parts of a platinum gold catalyst, 0.006-0.1 parts of an inhibitor and 50-100 parts of a diluent, and the catalyst is a solid acid catalyst. The silicone resin composition is applied to the production of mica plates, so that the curing and forming temperature can be effectively reduced, the pressing time can be shortened, the silicone resin composition has strong bonding force with mica paper, the delamination of the mica plate is effectively avoided, and the mica plate has excellent high-temperature water boiling delamination resistance.

Description

Technical Field

[0001] This invention relates to the field of organosilicon new material preparation technology, and in particular to silicone resin compositions, their preparation methods and applications. Background Technology

[0002] Organosilicon resins (also known as polysiloxanes) are a class of polymers whose backbone is composed of alternating silicon and oxygen atoms, with different organic groups linked to silicon atoms. Organosilicon resins contain both "organic groups" and "inorganic structures," a unique composition and molecular structure that combines the properties of organic substances with the functions of inorganic substances.

[0003] Organosilicon resins are highly cross-linked, network-structured polyorganosiloxanes. They are typically produced by hydrolyzing various mixtures of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or methylphenyldichlorosilane at relatively low temperatures in the presence of an organic solvent such as toluene, yielding acidic hydrolysates. The initial hydrolysis products are a mixture of cyclic, linear, and cross-linked polymers, usually containing a significant number of hydroxyl groups. The hydrolysates are washed with water to remove the acid, and the neutral primary condensate polymers are then thermally oxidized in air or further condensed in the presence of a catalyst, ultimately forming a highly cross-linked three-dimensional network structure.

[0004] Organosilicon resins and modified organosilicon resin products, with their excellent thermal oxidation stability, electrical insulation properties, weather resistance, water resistance, salt spray resistance, mildew resistance, and biocompatibility, are widely used in national defense, electrical industry, leather industry, light industrial products, rubber and plastics, food hygiene, and other industries, playing an irreplaceable role. my country's organosilicon industry has developed significantly since the early 1950s, making great strides in material properties, mechanisms, and applications. Compared with advanced countries, my country's technological gap is relatively small, but the gap in application is significant. With the increasing demand for high-temperature resistant materials, organosilicon polymers, as a class of distinctive materials, can be modified and matched with organic resins and inorganic materials to achieve structural-functional integration, showing great promise for applications in high-tech industries and cutting-edge fields.

[0005] Polymethyl silicone resin is generally composed of SiO2 3 / 2 CH3SiO 3 / 2 (CH3)3SiO 2 / 2 (CH)SiO 1 / 2Polymethylsilicone resin is a copolymer composed of siloxane chains. Using raw materials with only two or fewer methyl groups attached to each silicon atom (such as methyltrichlorosilane and dimethyldichlorosilane), a network structure of polymethylsilicone resin can be prepared, which transforms into an insoluble and infusible product upon heating. Polymethylsilicone resin exhibits high heat resistance and strong oxidation resistance. When methylsilicone resin is formed into sheet samples, it remains undamaged even when heated to 550°C in a vacuum or to 500°C in a hydrogen stream, and remains infusible over a long period. Mica sheets made from it show almost no smoke when heated to 600°C–700°C.

[0006] With the rapid rise of the new energy industry, the energy density of power batteries, as a core component, is also increasing, bringing with it growing safety risks that are receiving increasing attention from the new energy vehicle industry. To ensure passenger safety and provide drivers with sufficient escape time, covering the power battery with a mica sheet has become an increasingly popular choice for new energy vehicle manufacturers. Mica sheets are made by coating mica paper with a toluene solution of silicone resin and then curing it through hot pressing. Traditional silicone resin mainly relies on the condensation between residual hydroxyl groups at high temperatures for curing. This method suffers from drawbacks such as high pressing temperature and long pressing time, resulting in low production efficiency and high energy consumption. Furthermore, the hydrolysis of methylchlorosilane requires a large amount of toluene and generates a large amount of waste acid, causing significant environmental pollution.

[0007] Therefore, there is an urgent need for a silicone resin composition, its preparation method, and its application to solve the above problems. Summary of the Invention

[0008] The purpose of this invention is to provide a silicone resin composition, its preparation method, and its application. Applying the silicone resin composition of this invention to the production of mica board can effectively reduce the curing temperature and shorten the pressing time. At the same time, the silicone resin composition of this invention has a strong bonding force with mica paper, effectively avoiding delamination of the mica board, and has excellent resistance to delamination when boiled in high temperature water.

[0009] To achieve the above objectives, the present invention provides a silicone resin composition, wherein, by weight, the raw materials include 70-90 parts of methyltrialkoxysilane, 1-10 parts of vinyltrialkoxysilane, 1.5-15 parts of trialkoxyhydrosilane, 3-15 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 30-50 parts of compatibilizer, 40-70 parts of deionized water, 3-10 parts of catalyst, 0.02-0.7 parts of platinum catalyst, 5-20 parts of n-butyl titanate, 0.006-0.1 parts of inhibitor, and 50-100 parts of diluent, wherein the catalyst is a solid acid catalyst.

[0010] Compared with the prior art, the present invention has the following beneficial effects:

[0011] (1) This invention uses methyltrialkoxysilane as the main raw material for preparing silicone resin compositions. Based on this, vinyltrialkoxysilane, trialkoxyhydrosilane, and 3-glycidyl etheroxypropyltrimethoxysilane are introduced, resulting in the presence of both vinyl and active hydrogen groups in the main structure of the silicone resin composition. These two groups can undergo hydrosilylation under certain conditions. The reaction conditions are milder than the dehydration condensation between hydroxyl groups, thus effectively reducing the curing temperature and time. Simultaneously, 3-glycidyl etheroxypropyltrimethoxysilane further increases the polarity of the silicone resin system of this invention, making it easier to bond with mica paper. Therefore, it effectively avoids delamination of the mica board due to weak bonding with the silicone resin composition. Furthermore, the above-mentioned silane substances do not require toluene as a solvent during hydrolysis, making it more environmentally friendly.

[0012] (2) The tetrabutyl titanate introduced into the silicone resin composition system of the present invention can react with the residual hydroxyl groups in the silicone resin system, and can also react with the hydroxyl groups on the surface of mica paper, so as to further increase the bonding force between the silicone resin composition of the present invention and the mica paper, thereby improving the high temperature boiling delamination performance of the mica board.

[0013] (3) The present invention uses a solid acid catalyst to replace traditional liquid catalysts such as hydrochloric acid and sulfuric acid for the preparation of silicone resin, which facilitates the separation of the catalyst from the organosilicon resin after preparation, effectively reduces the generation of acid water, and is more environmentally friendly.

[0014] In summary, applying the silicone resin composition of this invention to the production of mica boards can effectively reduce the curing temperature and shorten the pressing time. It also exhibits strong adhesion to mica paper, effectively preventing delamination of the mica board and providing excellent resistance to high-temperature boiling and delamination. Furthermore, the preparation process requires little or no toluene, resulting in less acidic water and making it safer and more environmentally friendly.

[0015] As a preferred embodiment, the methyltrialkoxysilane of the present invention is selected from at least one of methyltrimethoxysilane and methyltriethoxysilane. The vinyltrialkoxysilane of the present invention is selected from at least one of vinyltrimethoxysilane and vinyltriethoxysilane. The trialkoxyhydrosilane of the present invention is selected from at least one of trimethoxyhydrosilane and triethoxyhydrosilane.

[0016] As a preferred technical solution, the solid acid catalyst of the present invention has an acid capacity ≥3.2 mmol / mg, a particle size of 16 mesh to 50 mesh, a bulk density of 0.55 g / ml to 0.65 g / ml, and a specific surface area ≥20 m². 2 / g.

[0017] As a preferred technical solution, the effective platinum content in the platinum catalyst of the present invention is 2800ppm to 3200ppm.

[0018] As a preferred technical solution, the compatibilizer of the present invention is selected from at least one of methanol, ethanol, and isopropanol.

[0019] As a preferred technical solution, the inhibitor of the present invention is selected from at least one of alkynyl alcohols, maleic esters, fumarates and tetramethyltetravinylcyclotetrasiloxane.

[0020] As a preferred technical solution, the diluent of the present invention is selected from at least one of alcohol compounds, benzene compounds, and ester compounds.

[0021] As a preferred embodiment, the alcohol compounds of the present invention are selected from at least one of methanol and ethanol. The benzene compounds of the present invention are selected from at least one of toluene and xylene. The ester compounds of the present invention are selected from ethyl acetate.

[0022] A second aspect of the present invention provides a method for preparing the aforementioned silicone resin composition, comprising:

[0023] (2) Preparation of silicone resin-based adhesive: The formula amounts of methyltrialkoxysilane, vinyltrialkoxysilane, trialkoxyhydrosilane, 3-glycidyl etheroxypropyltrimethoxysilane, compatibilizer, deionized water and catalyst are added to the reaction vessel and reacted at 65℃~75℃ for 3h~5h. Then the catalyst is removed by filtration and finally treated under vacuum for 1.5h~3h to obtain silicone resin-based adhesive.

[0024] (2) Preparation of silicone resin composition: Silicone resin base glue and titanate n-butyl ester are put into a reaction vessel and reacted at 110℃~150℃ for 3h~5h. The temperature is then lowered to 60℃~80℃ and de-distilled under vacuum until no obvious liquid is distilled out. After cooling to room temperature, inhibitor, diluent and platinum catalyst are added and stirred to obtain silicone resin composition.

[0025] This invention first involves hydrolyzing formulated amounts of methyltrialkoxysilane, vinyltrialkoxysilane, trialkoxyhydrosilane, and 3-glycidyl etheroxypropyltrimethoxysilane in the presence of a solid acid catalyst to obtain the corresponding silanols. The solid acid catalyst is then removed by filtration, followed by a condensation reaction under vacuum to obtain a silicone resin-based adhesive containing vinyl and active hydrogen groups. Reacting the silicone resin-based adhesive with n-butyl titanate under specific conditions effectively removes residual hydroxyl groups from the silicone resin-based adhesive system. Inhibitors, diluents, and a platinum catalyst are then added and stirred to obtain a silicone resin composition. The silicone resin composition prepared by the above method contains vinyl and active hydrogen groups in its structure. Under certain temperature and in the presence of a platinum catalyst, it undergoes a hydrosilylation reaction, effectively reducing the curing time and temperature of the silicone resin. 3-glycidyl etheroxypropyltrimethoxysilane increases the polarity of the silicone resin composition system of this invention, increasing its adhesion to mica paper. Furthermore, tetrabutyl titanate can react with the hydroxyl groups present on mica paper to form chemical bonds, further enhancing the bonding force between the silicone rubber resin system of this invention and mica paper, thereby improving the high-temperature water boiling delamination resistance of mica paper.

[0026] A third aspect of this invention provides the application of the aforementioned silicone resin composition or the silicone resin composition prepared according to the aforementioned method in the preparation of mica sheets. Applying the silicone resin composition of this invention to the preparation of mica sheets can effectively prevent delamination of the mica sheets and improve their resistance to delamination during high-temperature boiling. Detailed Implementation

[0027] The silicone resin composition of the present invention, by weight, comprises 70 to 90 parts of methyltrialkoxysilane, 1 to 10 parts of vinyltrialkoxysilane, 1.5 to 15 parts of trialkoxyhydrosilane, 3 to 15 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 30 to 50 parts of compatibilizer, 40 to 70 parts of deionized water, 3 to 10 parts of catalyst, 0.02 to 0.7 parts of platinum catalyst, 5 to 20 parts of tetrabutyl titanate, 0.006 to 0.1 parts of inhibitor, and 50 to 100 parts of diluent.

[0028] The weight percentage of the methyltrialkoxysilane of the present invention may be, but is not limited to, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, or 90 parts. The methyltrialkoxysilane of the present invention may be selected from at least one of methyltrimethoxysilane and methyltriethoxysilane. Methyltrialkoxysilane is the main raw material for forming the main structure of the silicone resin of the present invention.

[0029] The vinyltrialkoxysilane of the present invention can be, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts by weight. The vinyltrialkoxysilane of the present invention may be selected from at least one of vinyltrimethoxysilane and vinyltriethoxysilane. The trialkoxyhydrosilane of the present invention can be, but is not limited to, 1.5 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts by weight. The trialkoxyhydrosilane of the present invention may be selected from at least one of trimethoxyhydrosilane and triethoxyhydrosilane. The present invention enriches the structure of the silicone resin system by introducing vinyltrialkoxysilane and trialkoxyhydrosilane into methyltrimethoxysilane. Simultaneously, the introduced vinyl groups and active hydrogen can undergo an addition reaction under certain conditions, thereby effectively improving the adhesion between silicone resin systems.

[0030] The weight parts of 3-glycidyl etheroxypropyltrimethoxysilane of the present invention can be, but are not limited to, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 parts. The addition of 3-glycidyl etheroxypropyltrimethoxysilane can further increase the polarity of the silicone resin system of the present invention, thereby improving the adhesion between the silicone resin composition of the present invention and mica paper.

[0031] The compatibilizer of the present invention can be, but is not limited to, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, or 50 parts by weight. The compatibilizer can be selected from at least one of methanol, ethanol, and isopropanol. The deionized water of the present invention can be, but is not limited to, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts by weight.

[0032] The catalyst of this invention can be, but is not limited to, 3, 4, 5, 6, 7, 8, 9, or 10 parts by weight. The catalyst of this invention is a solid catalyst with an acid capacity ≥ 3.2 mmol / mg, a particle size of 16-50 mesh, a bulk density of 0.55 g / ml-0.65 g / ml, and a specific surface area ≥ 20 m². 2 / g. Using the solid acid catalyst of the above specifications, the hydrolysis reactions of methyltrialkoxysilane, vinyltrialkoxysilane, trialkoxyhydrosilane, and 3-glycidyl etheroxypropyltrimethoxysilane of the present invention can be effectively promoted to generate the corresponding silanols. Furthermore, the catalyst can be effectively removed by filtration after the hydrolysis reaction, eliminating the need for repeated water washing before subsequent polycondensation reactions. Therefore, using a solid acid catalyst improves reaction efficiency and effectively reduces the generation of acidic water, making it more environmentally friendly. Specifically, the catalyst of the present invention can be a strongly acidic cationic sulfonic acid type solid acid catalyst. As an example, the catalyst of the present invention can be HND-33 from Jiangyin Nanda Synthetic Chemical Co., Ltd., but is not limited to this.

[0033] The platinum catalyst of the present invention can be, but is not limited to, 0.02 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, or 0.7 parts by weight. The effective platinum content in the platinum catalyst of the present invention is 2800 ppm to 3200 ppm. As an example, the effective platinum content in the platinum catalyst of the present invention can be, but is not limited to, 2800 ppm, 2850 ppm, 2900 ppm, 2950 ppm, 3000 ppm, 3050 ppm, 3100 ppm, 3150 ppm, or 3200 ppm. The platinum catalyst can be, but is not limited to, chloroplatinic acid, chloroplatinous acid, Castells catalyst, or Speier catalyst. As an example, the platinum catalyst of the present invention is selected from Castells catalysts.

[0034] The weight percentage of n-butyl titanate in this invention can be, but is not limited to, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 parts. This invention introduces n-butyl titanate into a silicone rubber system. N-butyl titanate can react with hydroxyl groups in the silicone resin system to remove residual hydroxyl groups, and can also react with hydroxyl groups on the surface of mica paper. Therefore, the introduction of n-butyl titanate can improve the bonding strength between the silicone resin system and the mica paper, thereby improving its resistance to high-temperature boiling and delamination.

[0035] The weight parts of the inhibitor of the present invention may be, but are not limited to, 0.006 parts, 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, or 0.1 parts. The inhibitor is selected from at least one of alkynyl alcohols, maleic esters, fumarates, and tetramethyltetravinylcyclotetrasiloxane. Specifically, alkynyl alcohols may be, but are not limited to, at least one of 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol, and 3-phenyl-1-butyn-3-ol. Maleic esters may be, but are not limited to, at least one of dimethyl maleate, diethyl maleate, diphenyl maleate, diallyl maleate, and di(2-methoxyethyl) maleate. Fumarate may be, but is not limited to, diallyl fumarate.

[0036] The diluent of the present invention can be, but is not limited to, 50, 60, 70, 80, 90, or 100 parts by weight. The diluent is selected from at least one of alcohols, benzenes, and esters. Specifically, the alcohol is selected from at least one of methanol and ethanol, the benzene is selected from at least one of toluene and xylene, and the ester is selected from ethyl acetate. As an example, the diluent of the present invention is selected from ethyl acetate.

[0037] The preparation method of the silicone resin composition of the present invention includes (1) preparing silicone resin base glue: adding the formulated amounts of methyltrialkoxysilane, vinyltrialkoxysilane, trialkoxyhydrosilane, 3-glycidyl etheroxypropyltrimethoxysilane, compatibilizer, deionized water and catalyst into a reaction vessel and reacting at 65℃~75℃ for 3h~5h, then filtering to remove the catalyst, and finally treating under vacuum conditions for 1.5h~3h to obtain silicone resin base glue; (2) preparing silicone resin composition: adding silicone resin base glue and tetrabutyl titanate into a reaction vessel and reacting at 110℃~150℃ for 3h~5h, cooling to 60℃~80℃ and performing de-lowering treatment under vacuum conditions until no obvious liquid is distilled out, then cooling to room temperature and adding inhibitor, diluent and platinum catalyst and stirring to mix evenly to obtain silicone resin composition.

[0038] Specifically, in step (1), the reaction temperature can be, but is not limited to, 65℃, 66℃, 67℃, 68℃, 69℃, 70℃, 71℃, 72℃, 73℃, 74℃, or 75℃. The reaction time can be, but is not limited to, 3h, 3.5h, 4h, 4.5h, or 5h. The vacuum degree under vacuum conditions can be, but is not limited to, -0.09MPa. The vacuum treatment time can be, but is not limited to, 1.5h, 2h, 2.5h, or 3h.

[0039] In step (2), the reaction temperature can be, but is not limited to, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, or 150℃. The reaction time can be, but is not limited to, 3h, 3.5h, 4h, 4.5h, or 5h. The vacuum degree under vacuum conditions can specifically be -0.09MPa, but is not limited to this.

[0040] The silicone resin composition of the present invention can be used in the preparation of mica boards.

[0041] As an example, in use, the silicone resin composition is first diluted with a diluent to a solid content of 50%, and then evenly coated onto a 160g / cm² surface. 2 Mica paper, with an average adhesive coating of approximately 3%, is dried in a 75°C oven for 2 minutes to remove solvent, resulting in coated mica paper. Then, 20 layers of coated mica paper are stacked in the same direction and placed in a flat vulcanizing machine, pressed at 150°C and 30 MPa for 30 minutes. After removal and cooling to room temperature, a mica board is obtained. During the vulcanization and pressing process, hydrosilylation reactions can occur between the adhesives, which are faster than traditional hydroxyl-to-hydroxyl dehydration condensation. Therefore, the silicone resin composition of this invention can effectively reduce the pressing time and temperature in the preparation of mica boards. It should be noted that this is only one example of the application of the silicone resin of this invention in mica board production, but it is not limited thereto. That is, the solid content of the silicone resin composition of this invention, the physical properties of the mica board, the temperature and time of solvent removal, the number of stacked layers of mica paper, the pressing temperature, pressure, and time, etc., can be adjusted according to actual process requirements, and all such conventional adjustments are within the scope of protection of this invention.

[0042] To better illustrate the purpose, technical solution, and beneficial effects of this invention, the invention will be further described below with reference to specific embodiments. It should be noted that the methods described below are further explanations of this invention and should not be construed as limiting it.

[0043] In the embodiments and comparative examples of this invention, catalyst HND-33 was purchased from Jiangyin Nanda Synthetic Chemical Co., Ltd.; SH-9502 was purchased from Hubei Longsheng Sihai New Materials Co., Ltd. All other raw materials not described herein are commercially available.

[0044] Example 1

[0045] This embodiment provides a silicone resin composition, which, by weight, comprises 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrosilane, 15 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 40 parts of ethanol, 60 parts of deionized water, 7 parts of catalyst HND-33, 5 parts of n-butyl titanate, 0.09 parts of 1-ethynylcyclohexanol, 60 parts of ethyl acetate, and 0.2 parts of platinum catalyst (with an effective platinum content of 3000 ppm).

[0046] The method for preparing the silicone resin composition in this embodiment includes:

[0047] (1) Preparation of silicone resin-based adhesive: The prescribed amounts of methyltrimethoxysilane, vinyltrimethoxysilane, trimethoxyhydrosilane, 3-glycidyl etheroxypropyltrimethoxysilane, ethanol, deionized water, and catalyst HND-33 were added to a reaction vessel and reacted at 70°C for 4 hours. Then, the catalyst HND-33 was removed by filtration, and finally, the mixture was treated under vacuum for 2.5 hours to obtain silicone resin-based adhesive.

[0048] (2) Preparation of silicone resin composition: Silicone resin base glue and titanate n-butyl ester are added into the reaction vessel and reacted at 130°C for 3 hours. The temperature is then lowered to 70°C and de-distilled under vacuum until no obvious liquid is distilled out. After cooling to room temperature, 1-ethynylcyclohexanol, ethyl acetate and platinum catalyst are added in sequence and stirred to obtain silicone resin composition.

[0049] Application of silicone resin composition in mica board preparation: The silicone resin composition obtained in this example was diluted with ethyl acetate to a solid content of 50%, and uniformly coated onto a 160g / cm² mica substrate. 2 Mica paper is coated with an average amount of adhesive of 3% and then desolventized in a 75°C oven for 2 minutes to obtain coated mica paper. Then, 20 layers of coated mica paper are stacked in the same direction and placed in a flat vulcanizing machine. The paper is pressed at 150°C and 30MPa for 30 minutes, then removed and cooled to room temperature to obtain mica board.

[0050] Example 2

[0051] This embodiment provides a silicone resin composition, which, by weight, comprises 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrosilane, 10 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 40 parts of ethanol, 60 parts of deionized water, 7 parts of catalyst HND-33, 5 parts of tetrabutyl titanate, 0.09 parts of 1-ethynylcyclohexanol, 60 parts of ethyl acetate, and 0.2 parts of platinum catalyst (with an effective platinum content of 3000 ppm).

[0052] The preparation method of the silicone resin composition in this embodiment is the same as that in Example 1.

[0053] The specific application of the silicone resin composition in the preparation of mica board in this embodiment is the same as in Example 1.

[0054] Example 3

[0055] This embodiment provides a silicone resin composition, which, by weight, comprises 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrosilane, 5 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 40 parts of ethanol, 60 parts of deionized water, 7 parts of catalyst HND-33, 5 parts of n-butyl titanate, 0.09 parts of 1-ethynylcyclohexanol, 60 parts of ethyl acetate, and 0.2 parts of platinum catalyst (with an effective platinum content of 3000 ppm).

[0056] The preparation method of the silicone resin composition in this embodiment is the same as that in Example 1.

[0057] The specific application of the silicone resin composition in the preparation of mica board in this embodiment is the same as in Example 1.

[0058] Example 4

[0059] This embodiment provides a silicone resin composition, which, by weight, comprises 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrosilane, 15 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 40 parts of ethanol, 60 parts of deionized water, 7 parts of catalyst HND-33, 15 parts of n-butyl titanate, 0.09 parts of 1-ethynylcyclohexanol, 60 parts of ethyl acetate, and 0.2 parts of platinum catalyst (with an effective platinum content of 3000 ppm).

[0060] The preparation method of the silicone resin composition in this embodiment is the same as that in Example 1.

[0061] The specific application of the silicone resin composition in the preparation of mica board in this embodiment is the same as in Example 1.

[0062] Example 5

[0063] This embodiment provides a silicone resin composition, which, by weight, comprises 80 parts methyltriethoxysilane, 9 parts vinyltriethoxysilane, 15 parts trimethoxyhydrosilane, 15 parts 3-glycidyl etheroxypropyltrimethoxysilane, 40 parts ethanol, 60 parts deionized water, 7 parts catalyst HND-33, 10 parts n-butyl titanate, 0.1 parts 1-ethynylcyclohexanol, 52 parts ethyl acetate, and 0.05 parts platinum catalyst (platinum effective content is 3000 ppm).

[0064] The preparation method of the silicone resin composition in this embodiment is the same as that in Example 1.

[0065] The specific application of the silicone resin composition in the preparation of mica board in this embodiment is the same as in Example 1.

[0066] Comparative Example 1

[0067] The comparative example used commercially available silicone resin, model SH-9502.

[0068] Application of silicone resin composition in mica board preparation: Commercially available SH-9502 silicone resin with a solid content of 50% was uniformly coated onto a 160g / cm² substrate. 2 Mica paper is coated with an average amount of adhesive of 3% and then desolventized in a 75°C oven for 2 minutes to obtain coated mica paper. Then, 20 layers of coated mica paper are stacked in the same direction and placed in a flat vulcanizing machine. The paper is pressed at 150°C and 30MPa for 30 minutes, then removed and cooled to room temperature to obtain mica board.

[0069] Comparative Example 2

[0070] The comparative example used commercially available silicone resin, model SH-9502.

[0071] Commercially available SH-9502 silicone resin with a solid content of 50% was evenly coated onto a 160g / cm² layer. 2 Mica paper is coated with an average amount of adhesive of 3% and then desold in a 75°C oven for 2 minutes to obtain coated mica paper. Then, 20 layers of coated mica paper are stacked in the same direction and placed in a flat vulcanizing machine. The paper is pressed at 220°C and 30MPa for 30 minutes, then removed and cooled to room temperature to obtain mica board.

[0072] Comparative Example 3

[0073] The comparative example used commercially available silicone resin, model SH-9502.

[0074] Commercially available SH-9502 silicone resin with a solid content of 50% was evenly coated onto a 160g / cm² layer. 2 Mica paper is coated with an average amount of adhesive of 3% and then desold in a 125°C oven for 2 minutes to obtain coated mica paper. Then, 20 layers of coated mica paper are stacked in the same direction and placed in a flat vulcanizing machine. The paper is pressed at 220°C and 30MPa for 90 minutes, then removed and cooled to room temperature to obtain mica board.

[0075] Comparative Example 4

[0076] The comparative example used commercially available silicone resin, model SH-9502.

[0077] Commercially available SH-9502 silicone resin with a solid content of 50% was evenly coated onto a 160g / cm² layer. 2Mica paper is coated with an average amount of adhesive of 3% and desold in a 125°C oven for 2 minutes to obtain coated mica paper. Then, 20 layers of coated mica paper are stacked in the same direction and placed in a flat vulcanizing machine. The paper is pressed at 220°C and 30MPa for 180 minutes, then removed and cooled to room temperature to obtain mica board.

[0078] Comparative Example 5

[0079] This comparative example provides a silicone resin composition, which, by weight, comprises 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrosilane, 15 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 40 parts of ethanol, 60 parts of deionized water, 7 parts of catalyst HND-33, 0.09 parts of 1-ethynylcyclohexanol, 60 parts of ethyl acetate, and 0.2 parts of platinum catalyst (with an effective platinum content of 3000 ppm).

[0080] This comparative example describes a method for preparing a silicone resin composition, comprising:

[0081] (1) Preparation of silicone resin-based adhesive: The prescribed amounts of methyltrimethoxysilane, vinyltrimethoxysilane, trimethoxyhydrosilane, 3-glycidyl etheroxypropyltrimethoxysilane, ethanol, deionized water, and catalyst HND-33 were added to a reaction vessel and reacted at 70°C for 4 hours. Then, the catalyst HND-33 was removed by filtration, and finally, the mixture was treated under vacuum for 2.5 hours to obtain silicone resin-based adhesive.

[0082] (2) Preparation of silicone resin composition: Silicone resin base glue, 1-ethynylcyclohexanol, ethyl acetate and platinum catalyst are stirred and mixed evenly at room temperature to obtain silicone resin composition.

[0083] The specific application of the silicone resin composition in the preparation of mica board in this comparative example is the same as that in Example 1.

[0084] Comparative Example 6

[0085] This comparative example provides a silicone resin composition, which, by weight, comprises 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrosilane, 15 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 40 parts of ethanol, 60 parts of deionized water, 7 parts of catalyst HND-33, 5 parts of isopropyl titanate, 0.09 parts of 1-ethynylcyclohexanol, 60 parts of ethyl acetate, and 0.2 parts of platinum catalyst (with an effective platinum content of 3000 ppm).

[0086] The preparation method of this comparative silicone resin composition is the same as that of Example 1.

[0087] The specific application of the silicone resin composition in the preparation of mica board in this comparative example is the same as that in Example 1.

[0088] Comparative Example 7

[0089] This comparative example provides a silicone resin composition, which, by weight, comprises 80 parts methyltrimethoxysilane, 9 parts vinyltrimethoxysilane, 15 parts trimethoxyhydrosilane, 40 parts ethanol, 60 parts deionized water, 7 parts catalyst HND-33, 5 parts isopropyl titanate, 0.09 parts 1-ethynylcyclohexanol, 60 parts ethyl acetate, and 0.2 parts platinum catalyst (platinum effective content is 3000 ppm).

[0090] The method for preparing the silicone resin composition of this comparative example includes:

[0091] (1) Preparation of silicone resin-based adhesive: The formula amounts of methyltrimethoxysilane, vinyltrimethoxysilane, trimethoxyhydrosilane, ethanol, deionized water and catalyst HND-33 are added to the reaction vessel and reacted at 70°C for 4 hours. Then, the catalyst HND-33 is removed by filtration and finally treated under vacuum for 2.5 hours to obtain silicone resin-based adhesive.

[0092] (2) Preparation of silicone resin composition: Silicone resin base glue and titanate n-butyl ester are added into the reaction vessel and reacted at 130°C for 3 hours. The temperature is then lowered to 70°C and de-distilled under vacuum until no obvious liquid is distilled out. After cooling to room temperature, 1-ethynylcyclohexanol, ethyl acetate and platinum catalyst are added in sequence and stirred to obtain silicone resin composition.

[0093] The specific application of the silicone resin composition in the preparation of mica board in this comparative example is the same as that in Example 1.

[0094] Comparative Example 8

[0095] This comparative example provides a silicone resin composition, which, by weight, comprises 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrosilane, 15 parts of γ-aminopropyltrimethoxysilane, 40 parts of ethanol, 60 parts of deionized water, 7 parts of catalyst HND-33, 5 parts of isopropyl titanate, 0.09 parts of 1-ethynylcyclohexanol, 60 parts of ethyl acetate, and 0.2 parts of platinum catalyst (with an effective platinum content of 3000 ppm).

[0096] The preparation method of this comparative silicone resin composition is the same as that of Example 1.

[0097] The specific application of the silicone resin composition in the preparation of mica board in this comparative example is the same as that in Example 1.

[0098] The mica sheets from Examples 1-6 and Comparative Examples 1-8 were cut into 2cm × 2cm pieces. The delamination of the mica sheets during the cutting process was observed. Then, five pieces of each cut mica sheet were placed in boiling water and boiled for 30 minutes, and the delamination was observed again. The test results are shown in Table 1.

[0099] Table 1 shows the performance test results of the silicone resin compositions of Examples 1-6 and Comparative Examples 1-8 in the preparation of mica boards.

[0100]

[0101]

[0102] The test results are shown in Table 1. A comparison of Examples 1-5 and Comparative Examples 1-4 reveals that applying the silicone resin composition obtained in this invention to the production of mica sheets results in better water-boiling resistance. Comparative Examples 1-4 show that when using commercially available silicone resin, increasing the solvent drying temperature to 125°C, the pressing temperature to 220°C, and the pressing time to 180 minutes is necessary to prevent delamination of the cut mica sheets. However, in the water-boiling resistance test, 20% of the mica sheets still exhibited delamination. Therefore, in the production of mica sheets, the silicone resin composition of this invention requires a shorter pressing time, a lower pressing temperature, and exhibits superior high-temperature water-boiling resistance and delamination performance compared to currently available silicone resins.

[0103] Comparing Example 1 with Comparative Example 5, it can be seen that the absence of tetrabutyl titanate resulted in 20% delamination of the mica board during the water boiling resistance test. This indicates that the lack of tetrabutyl titanate weakens the bonding force between the silicone resin composition of the present invention and the mica paper, thereby affecting its high-temperature water boiling resistance.

[0104] Comparing Example 1 with Comparative Example 6, it can be seen that when tetrabutyl titanate is replaced with isopropyl titanate, 20% of the mica board shows delamination, indicating that tetrabutyl titanate makes the bonding force between the silicone resin composition of the present invention and the mica paper better than that of isopropyl titanate, and therefore its high-temperature boiling resistance is also better than that of isopropyl titanate.

[0105] Comparing Example 1 with Comparative Example 7, it can be seen that when 3-glycidyl etheroxypropyltrimethoxysilane is missing, 20% of the mica board shows delamination, indicating that the lack of 3-glycidyl etheroxypropyltrimethoxysilane weakens the bonding force between the silicone resin composition of the present invention and the mica paper, thereby affecting its performance.

[0106] Comparing Example 1 with Comparative Example 8, it can be seen that when 3-glycidyl etheroxypropyltrimethoxysilane was replaced with γ-aminopropyltrimethoxysilane, 30% of the mica boards showed delamination, indicating that γ-aminopropyltrimethoxysilane was significantly less effective than 3-glycidyl etheroxypropyltrimethoxysilane in improving the water resistance of mica boards.

[0107] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, it is not limited to those listed in the embodiments. Those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A silicone resin composition, characterized in that, The raw materials, by weight, include 70-90 parts of methyltrialkoxysilane, 1-10 parts of vinyltrialkoxysilane, 1.5-15 parts of trialkoxyhydrosilane, 3-15 parts of 3-glycidyl etheroxypropyltrimethoxysilane, 30-50 parts of compatibilizer, 40-70 parts of deionized water, 5-20 parts of n-butyl titanate, 3-10 parts of catalyst, 0.02-0.7 parts of platinum catalyst, 0.006-0.1 parts of inhibitor, and 50-100 parts of diluent, wherein the catalyst is a solid acid catalyst.

2. The silicone resin composition according to claim 1, characterized in that, The methyltrialkoxysilane is selected from at least one of methyltrimethoxysilane and methyltriethoxysilane, the vinyltrialkoxysilane is selected from at least one of vinyltrimethoxysilane and vinyltriethoxysilane, and the trialkoxyhydrosilane is selected from at least one of trimethoxyhydrosilane and triethoxyhydrosilane.

3. The silicone resin composition according to claim 1, characterized in that, The solid acid catalyst has an acid capacity ≥3.2 mmol / g, a particle size of 16-50 mesh, a bulk density of 0.55 g / ml-0.65 g / ml, and a specific surface area ≥20 m². 2 / g.

4. The silicone resin composition according to claim 1, characterized in that, The effective platinum content in the platinum catalyst is 2800 ppm to 3200 ppm.

5. The silicone resin composition according to claim 1, characterized in that, The compatibilizer is selected from at least one of methanol, ethanol, and isopropanol.

6. The silicone resin composition according to claim 1, characterized in that, The inhibitor is selected from at least one of alkynyl alcohols, maleate esters, fumarate esters, and tetramethyltetravinylcyclotetrasiloxane.

7. The silicone resin composition according to claim 1, characterized in that, The diluent is selected from at least one of alcohols, benzenes, and esters.

8. The silicone resin composition according to claim 7, characterized in that, The alcohol compound is selected from at least one of methanol and ethanol, the benzene compound is selected from at least one of toluene and xylene, and the ester compound is selected from ethyl acetate.

9. The method for preparing the silicone resin composition according to any one of claims 1 to 8, characterized in that, include: (1) Preparation of silicone resin-based adhesive: The prescribed amounts of the methyltrialkoxysilane, the vinyltrialkoxysilane, the trialkoxyhydrosilane, the 3-glycidyl etheroxypropyltrimethoxysilane, the compatibilizer, the deionized water, and the catalyst are added to a reaction vessel and reacted at 65℃~75℃ for 3h~5h. Then the catalyst is removed by filtration, and finally the mixture is treated under vacuum for 1.5h~3h to obtain silicone resin-based adhesive. (2) Preparation of silicone resin composition: The silicone resin base glue and the titanate n-butyl ester are put into a reaction vessel and reacted at 110℃~150℃ for 3h~5h. The temperature is lowered to 60℃~80℃ and de-lowered under vacuum until no obvious liquid is distilled out. After cooling to room temperature, the inhibitor, the diluent and the platinum catalyst are added and stirred to obtain silicone resin composition.

10. The use of the silicone resin composition according to any one of claims 1 to 8 or the silicone resin composition prepared by the method according to claim 9 in the preparation of mica panels.

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