Silicone resin composition as well as preparation method and application thereof

Abstract

The invention provides a silicon resin composition as well as a preparation method and application thereof, and relates to the technical field of preparation of novel organic silicon materials. The silicon resin composition disclosed by the invention is prepared from the following raw materials in parts by weight: 70 to 90 parts of methyl trialkoxysilane, 1 to 10 parts of vinyl trialkoxysilane, 1.5 to 15 parts of trialkoxyhydrosilane, 3 to 15 parts of 3-glycidyl ether oxypropyl trimethoxy silane, 5 to 20 parts of tetrabutyl titanate, 30 to 50 parts of compatilizer, 40 to 70 parts of deionized water, 3 to 10 parts of catalyst, 0.02 to 0.7 part of platinum catalyst and 0.006 part of platinum catalyst. 0.1 part of an inhibitor and 50-100 parts of a diluent, and the catalyst is a solid acid catalyst. When the silicon resin composition is applied to production of the mica plate, the curing forming temperature can be effectively reduced, the pressing time can be shortened, meanwhile, the silicon resin composition has relatively strong binding force with mica paper, the layering condition of the mica plate is effectively avoided, and the silicon resin composition has excellent high-temperature water boiling layering resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of new organosilicon materials, and in particular to a silicone resin composition and a preparation method and application thereof. Background Art

[0002] Silicone resin (also known as polysiloxane) is a general term for a class of polymers whose skeletons are composed of alternately linked silicon atoms and oxygen atoms, and different organic groups are linked to silicon atoms. The structure of silicone resin contains both "organic groups" and "inorganic structures". This special composition and molecular structure makes it a combination of organic properties and inorganic functions.

[0003] Silicone resin is a highly cross-linked polysiloxane with a network structure. It is usually prepared by hydrolyzing various mixtures of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane or methylphenyldichlorosilane at a relatively low temperature in the presence of an organic solvent such as toluene to obtain an acidic hydrolyzate. The initial product of the hydrolysis is a mixture of cyclic, linear and cross-linked polymers, which usually also contains a considerable amount of hydroxyl groups. The hydrolyzate is washed with water to remove the acid, and the neutral primary polycondensate is further polycondensed by thermal oxidation in the air or in the presence of a catalyst to finally form a highly cross-linked three-dimensional network structure.

[0004] Silicone resin and modified silicone resin products are widely used in defense and military industry, electrical industry, leather industry, light industrial products, rubber and plastic, food hygiene and other industries due to their excellent thermal oxidation stability, electrical insulation performance, weather resistance, waterproof, salt spray resistance, mildew resistance, biocompatibility and other characteristics, playing an irreplaceable role. Since the early 1950s, my country's silicone industry has made great progress in material performance, mechanism and application. Compared with advanced countries, my country's technological gap is relatively small, but the gap in application is relatively large. With the continuous increase in the demand for high-temperature resistant materials, silicone polymers, as a type of material with outstanding characteristics, can be modified and matched with organic resins and inorganic materials to achieve structural and functional integration, and have broad application prospects in high-tech industries and cutting-edge fields.

[0005] Polymethyl silicone resin is generally composed of SiO 3 / 2 、CH3SiO 3 / 2 、(CH3)3SiO 2 / 2 、(CH)SiO 1 / 2A copolymer composed of siloxane chain segments. Using raw materials with only two or less methyl groups attached to each silicon atom (such as methyltrichlorosilane and dimethyldichlorosilane), a polymethyl silicone resin with a network structure can be obtained, which can be transformed into an insoluble and infusible product when heated. Polymethyl silicone resin has high heat resistance and strong oxidation resistance. Methyl silicone resin is made into a sheet sample, which will not be destroyed when heated to 550°C in a vacuum or to 500°C in a hydrogen flow, and will remain infusible for a long time. The mica sheet made from it will hardly smoke when heated to 600°C to 700°C.

[0006] With the rapid rise of the new energy industry, the energy density of power batteries, as core components, is getting higher and higher, and the resulting safety risks are increasingly valued by the new energy industry. In order to ensure the safety of passengers and provide drivers with sufficient escape time, coating the power battery with a layer of mica sheet special-shaped parts has become the choice of more and more new energy vehicle companies. Mica sheet is made by hot pressing and curing mica paper coated with a toluene solution of silicone resin. Traditional silicone resin is mainly cured by condensation between residual hydroxyl groups at high temperature. There are disadvantages of high pressing temperature and long pressing time, low production efficiency and high energy consumption. Methylchlorosilane requires a large amount of toluene in the hydrolysis process, and a large amount of waste acid is produced in the hydrolysis process, which pollutes the environment.

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

[0008] The purpose of the present invention is to provide a silicone resin composition and a preparation method and application thereof. The silicone resin composition of the present invention is applied to the production of mica boards, which can effectively reduce the curing molding temperature and shorten the pressing time. At the same time, the silicone resin composition of the present invention has a strong bonding force with mica paper, effectively avoiding the delamination of the mica board, and has excellent high-temperature boiling resistance and delamination performance.

[0009] To achieve the above-mentioned purpose, the present invention provides a silicone resin composition on the one hand, wherein the raw materials for preparation include, by weight, 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-glycidyloxypropyltrimethoxysilane, 30 to 50 parts of a compatibilizer, 40 to 70 parts of deionized water, 3 to 10 parts of a catalyst, 0.02 to 0.7 parts of a platinum catalyst, 5 to 20 parts of n-butyl titanate, 0.006 to 0.1 parts of an inhibitor and 50 to 100 parts of a diluent, and the catalyst is a solid acid catalyst.

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

[0011] (1) The present invention uses methyltrialkoxysilane as the main raw material for preparing the silicone resin composition, and on this basis introduces vinyltrialkoxysilane, trialkoxyhydrogensilane and 3-glycidyloxypropyltrimethoxysilane, so that vinyl and active hydrogen groups exist in the main structure of the silicone resin composition of the present invention at the same time. These two groups can undergo silylation reaction under certain conditions. The reaction conditions are milder than the dehydration condensation between hydroxyl groups, so the curing molding temperature and time can be effectively reduced. At the same time, 3-glycidyloxypropyltrimethoxysilane can further increase the polarity of the silicone resin system of the present invention, making it easier to combine with mica paper, thereby effectively avoiding the situation where the mica board is delaminated due to the loose combination with the silicone resin composition. In addition, the above-mentioned silane substances do not need to use toluene as a solvent during the hydrolysis process, which is more environmentally friendly.

[0012] (2) The n-butyl 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 also react with the hydroxyl groups on the surface of the mica paper 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 resistance and 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 and the silicone resin after preparation, can effectively reduce the generation of acid water, and is more environmentally friendly.

[0014] In summary, the silicone resin composition of the present invention is applied to the production of mica boards, which can effectively reduce the curing molding temperature and shorten the pressing time. At the same time, it has a strong bonding force with mica paper, effectively avoids the delamination of the mica board, and has excellent high-temperature boiling and delamination performance. In addition, no or less toluene is used in the preparation process, less acid water is generated, and it is safer and more environmentally friendly.

[0015] As a preferred technical solution, 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 trialkoxyhydrogensilane of the present invention is selected from at least one of trimethoxyhydrogensilane and triethoxyhydrogensilane.

[0016] As a preferred technical solution, the solid acid catalyst of the present invention has an acid capacity of ≥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 of ​​≥20 m 2 / g.

[0017] As a preferred technical solution, the effective content of platinum 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 acetylenic alcohol compounds, maleic acid esters, fumaric acid esters 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 technical solution, the alcohol compound of the present invention is selected from at least one of methanol and ethanol. The benzene compound of the present invention is selected from at least one of toluene and xylene. The ester compound of the present invention is selected from ethyl acetate.

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

[0023] (2) Preparation of silicone resin adhesive: Add the formulated amount of methyltrialkoxysilane, vinyltrialkoxysilane, trialkoxyhydrogensilane, 3-glycidyloxypropyltrimethoxysilane, compatibilizer, deionized water, and catalyst into a reaction kettle and react at 65° C. to 75° C. for 3 h to 5 h, then remove the catalyst by filtration, and finally treat under vacuum conditions for 1.5 h to 3 h to obtain a silicone resin adhesive;

[0024] (2) Preparation of silicone resin composition: silicone resin base glue and n-butyl titanate are placed in a reaction kettle and reacted at 110°C to 150°C for 3h to 5h, cooled to 60°C to 80°C and degassed under vacuum until no obvious liquid is distilled out, cooled to room temperature, and then inhibitors, diluents, and platinum catalysts are added and stirred to obtain a silicone resin composition.

[0025] The present invention firstly hydrolyzes the methyltrialkoxysilane, vinyltrialkoxysilane, trialkoxyhydrogensilane and 3-glycidyloxypropyltrimethoxysilane in the formula amount under the condition of solid acid catalyst to obtain corresponding silanol substances, then removes the solid acid catalyst by filtering, and then carries out polycondensation reaction under vacuum conditions to obtain a silicone resin base adhesive containing vinyl and active hydrogen groups in the structure. The silicone resin base adhesive is reacted with n-butyl titanate under certain conditions to effectively remove the residual hydroxyl groups in the silicone resin base adhesive system, and then an inhibitor, a diluent and a platinum catalyst are added and stirred to obtain a silicone resin composition. The silicone resin composition prepared by the above preparation method contains vinyl and active hydrogen groups in its structure, and undergoes a silylation reaction under a certain temperature and the condition of the presence of a Perkin catalyst, which can effectively reduce the curing time and curing temperature of the silicone resin, and 3-glycidyloxypropyltrimethoxysilane can increase the polarity of the silicone resin composition system of the present invention and increase its binding force with mica paper. In addition, n-butyl titanate can also react with the hydroxyl groups on the mica paper to form chemical bonds, further improving the bonding strength between the silicone rubber resin system of the present invention and the mica paper, thereby improving the high-temperature boiling resistance and delamination performance of the mica paper.

[0026] The third aspect of the present invention provides the use of the aforementioned silicone resin composition or the silicone resin composition prepared according to the aforementioned method for preparing the silicone resin composition in the preparation of mica boards. The silicone resin composition of the present invention is used in the preparation of mica boards to effectively avoid the delamination of the mica boards and improve their resistance to high temperature boiling delamination. DETAILED DESCRIPTION

[0027] The silicone resin composition of the present invention comprises, by weight, 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-glycidyloxypropyltrimethoxysilane, 30 to 50 parts of a compatibilizer, 40 to 70 parts of deionized water, 3 to 10 parts of a catalyst, 0.02 to 0.7 parts of a platinum catalyst, 5 to 20 parts of n-butyl titanate, 0.006 to 0.1 parts of an inhibitor and 50 to 100 parts of a diluent.

[0028] Wherein, the weight proportion of the methyltrialkoxysilane of the present invention can 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, and 90 parts. The methyltrialkoxysilane of the present invention can be selected from at least one of methyltrimethoxysilane and methyltriethoxysilane. Methyltrialkoxysilane is the main raw material for preparation to form the main structure of the silicone resin of the present invention.

[0029] The weight proportion of the vinyl trialkoxysilane 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, and 10 parts. The vinyl trialkoxysilane of the present invention can be selected from at least one of vinyl trimethoxysilane and vinyl triethoxysilane. The weight proportion of the trialkoxy hydrogen silane 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, and 15 parts. The trialkoxy hydrogen silane of the present invention can be selected from at least one of trimethoxy hydrogen silane and triethoxy hydrogen silane. The present invention enriches the structure of the silicone resin system of the present invention by introducing vinyl trialkoxy silane and trialkoxy hydrogen silane into methyl trimethoxy silane, and the vinyl introduced at the same time can undergo addition reaction with active hydrogen under certain conditions, thereby effectively improving the bonding force between the silicone resin systems.

[0030] The weight proportion of 3-glycidyloxypropyltrimethoxysilane of the present invention can be, but is not limited to, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts. The addition of 3-glycidyloxypropyltrimethoxysilane can further increase the polarity of the silicone resin system of the present invention, thereby facilitating the increase of the bonding strength between the silicone resin composition of the present invention and the mica paper.

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

[0032] The weight proportion of the catalyst of the present invention can be, but is not limited to, 3, 4, 5, 6, 7, 8, 9, or 10. The catalyst of the present invention is a solid catalyst, the acid capacity of the solid catalyst is ≥3.2 mmol / mg, the particle size is 16-50 mesh, the bulk density is 0.55 g / ml-0.65 g / ml, and the specific surface area is ≥20 m 2 / g. The solid acid catalyst of the above specifications can effectively promote the hydrolysis reaction of methyltrialkoxysilane, vinyltrialkoxysilane, trialkoxyhydrosilane and 3-glycidyloxypropyltrimethoxysilane of the present invention to generate corresponding silanol substances, and the catalyst can be effectively removed by filtering after the hydrolysis reaction, and subsequent polycondensation reaction can be carried out without repeated water washing. Therefore, the reaction efficiency is improved by using a solid acid catalyst, and the generation of acid water is effectively reduced, which is 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 of Jiangyin Nanda Synthetic Chemical Co., Ltd., but is not limited thereto.

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

[0034] The weight proportion of n-butyl titanate of the present invention can be, but is not limited to, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, and 20 parts. The present invention introduces n-butyl titanate into the silicone rubber system, and n-butyl titanate can react with the hydroxyl group in the silicone resin system to remove the residual hydroxyl group, and can also react with the hydroxyl group on the surface of the mica paper. Therefore, the introduction of n-butyl titanate can enhance the bonding force between the silicone resin system of the present invention and the mica paper, thereby enhancing its high temperature boiling resistance delamination performance.

[0035] The weight proportion of the inhibitor of the present invention can be, but is not limited to, 0.006, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1. The inhibitor is selected from at least one of alkynol compounds, maleic acid esters, fumaric acid esters, and tetramethyltetravinylcyclotetrasiloxane. Specifically, alkynol compounds can 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 acid esters can be, but are not limited to, at least one of dimethyl maleate, diethyl maleate, diphenyl maleate, diallyl maleate, and di(2-methoxyethyl) maleate. Fumaric acid esters can be, but are not limited to, diallyl fumarate.

[0036] The weight proportion of the diluent of the present invention can be, but is not limited to, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, and 100 parts. The diluent is selected from at least one of an alcohol compound, a benzene compound, and an ester compound. Specifically, 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. 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 comprises: (1) preparing a silicone resin base glue: adding a formula amount of methyltrialkoxysilane, vinyltrialkoxysilane, trialkoxyhydrogensilane, 3-glycidyloxypropyltrimethoxysilane, a compatibilizer, deionized water, and a catalyst into a reaction kettle and reacting at 65°C to 75°C for 3h to 5h, then removing the catalyst by filtering, and finally treating under vacuum conditions for 1.5h to 3h to obtain a silicone resin base glue; (2) preparing a silicone resin composition: adding a silicone resin base glue and n-butyl titanate into a reaction kettle and reacting at 110°C to 150°C for 3h to 5h, cooling to 60°C to 80°C, and performing a desulfurization treatment under vacuum conditions until no obvious liquid is distilled out, and then cooling to room temperature, adding an inhibitor, a diluent, and a platinum catalyst, stirring and mixing to obtain a silicone resin composition.

[0038] Specifically, in step (1), the reaction temperature can be, but is not limited to, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C. The reaction time can be, but is not limited to, 3h, 3.5h, 4h, 4.5h, 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, 3h.

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

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

[0041] As an example, when using, first dilute the silicone resin composition with a diluent to a glue solution with a solid content of 50%, and evenly apply it on a 160g / cm 2 mica paper, control the average coating amount of glue to about 3%, desolventize in a 75°C drying tunnel for 2 minutes, obtain glued mica paper, and then stack 20 layers of glued mica paper in the same direction, put it into a flat vulcanizer, press it at 150°C, 30MPa for 30 minutes, take it out, and cool it to room temperature to obtain a mica board. During the vulcanization pressing process, a silane-hydrogen addition reaction can occur between the glue liquids, and its reaction rate is faster than the traditional dehydration condensation between hydroxyls. Therefore, the silicone resin composition of the present invention is used in the preparation of mica boards to effectively reduce its pressing molding time and temperature. It should be noted that this is only an example of the application of the silicone resin of the present invention in the production of mica boards, but it is not limited to this. That is, the solid content of the silicone resin composition of the present invention, the physical properties of the mica board, the temperature and time of desolventization, the number of stacked layers of mica paper, the pressing temperature, pressure and time, etc. can be adjusted according to the actual process requirements, and the conventional adjustments made are all within the scope of protection of the present invention.

[0042] In order to better illustrate the purpose, technical scheme and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be noted that the following implementation method is a further explanation of the present invention and should not be used as a limitation of the present invention.

[0043] In the examples and comparative examples of the present invention, the catalyst HND-33 was purchased from Jiangyin Nanda Synthetic Chemical Co., Ltd.; SH-9502 was purchased from Hubei Longsheng Sihai New Materials Co., Ltd. The remaining raw materials not described here can be obtained from common commercial sources.

[0044] Example 1

[0045] The present embodiment provides a silicone resin composition, in which the raw materials for preparation include, by weight, 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrogensilane, 15 parts of 3-glycidyloxypropyltrimethoxysilane, 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 (the effective content of platinum is 3000 ppm).

[0046] The preparation method of the silicone resin composition of this embodiment comprises:

[0047] (1) Preparation of silicone resin adhesive: adding a formula amount of methyltrimethoxysilane, vinyltrimethoxysilane, trimethoxyhydrogensilane, 3-glycidyloxypropyltrimethoxysilane, ethanol, deionized water, and catalyst HND-33 into a reaction kettle and reacting at 70° C. for 4 hours, then removing the catalyst HND-33 by filtration, and finally treating under vacuum conditions for 2.5 hours to obtain a silicone resin adhesive;

[0048] (2) Preparation of silicone resin composition: silicone resin base glue and n-butyl titanate are placed in a reaction kettle and reacted at 130° C. for 3 h, cooled to 70° C. and degased under vacuum conditions until no obvious liquid is distilled out, cooled to room temperature, 1-ethynylcyclohexanol, ethyl acetate, and platinum catalyst are added in sequence, stirred and mixed to obtain a silicone resin composition.

[0049] Application of silicone resin composition in the preparation of mica board: The silicone resin composition prepared in this embodiment is diluted with ethyl acetate to a glue solution with a solid content of 50%, and evenly coated on a 160g / cm 2 The mica paper is coated with glue at an average amount of 3%, and the solvent is removed in a drying oven at 75°C for 2 minutes to obtain the coated mica paper. Then 20 layers of the coated mica paper are stacked in the same direction, put into a flat vulcanizer, pressed at 150°C and 30MPa for 30 minutes, taken out, and cooled to room temperature to obtain a mica board.

[0050] Example 2

[0051] The present embodiment provides a silicone resin composition, in which the raw materials for preparation include, by weight, 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrogensilane, 10 parts of 3-glycidyloxypropyltrimethoxysilane, 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 (the effective content of platinum is 3000 ppm).

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

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

[0054] Example 3

[0055] The present embodiment provides a silicone resin composition, in which the raw materials for preparation include, by weight, 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrogensilane, 5 parts of 3-glycidyloxypropyltrimethoxysilane, 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 (the effective content of platinum is 3000 ppm).

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

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

[0058] Example 4

[0059] The present embodiment provides a silicone resin composition, in which the raw materials for preparation include, by weight, 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrogensilane, 15 parts of 3-glycidyloxypropyltrimethoxysilane, 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 (the effective content of platinum is 3000 ppm).

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

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

[0062] Example 5

[0063] The present embodiment provides a silicone resin composition, in which the raw materials for preparation include, by weight, 80 parts of methyltriethoxysilane, 9 parts of vinyltriethoxysilane, 15 parts of trimethoxyhydrogensilane, 15 parts of 3-glycidyloxypropyltrimethoxysilane, 40 parts of ethanol, 60 parts of deionized water, 7 parts of catalyst HND-33, 10 parts of n-butyl titanate, 0.1 parts of 1-ethynylcyclohexanol, 52 parts of ethyl acetate and 0.05 parts of platinum catalyst (the effective content of platinum is 3000 ppm).

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

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

[0066] Comparative Example 1

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

[0068] Application of silicone resin composition in the preparation of mica board: SH-9502 silicone resin with a solid content of 50% is evenly coated on 160g / cm 2 The mica paper is coated with glue at an average amount of 3%, and the solvent is removed in a drying oven at 75°C for 2 minutes to obtain the coated mica paper. Then 20 layers of the coated mica paper are stacked in the same direction, put into a flat vulcanizer, pressed at 150°C and 30MPa for 30 minutes, taken out, and cooled to room temperature to obtain a mica board.

[0069] Comparative Example 2

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

[0071] The commercially available SH-9502 silicone resin with a solid content of 50% was evenly coated on a 160g / cm 2 The mica paper is coated with an average adhesive amount of 3%, and the solvent is removed in a 75°C drying oven for 2 minutes to obtain the coated mica paper. Then 20 layers of the coated mica paper are stacked in the same direction, put into a flat vulcanizer, pressed at 220°C and 30MPa for 30 minutes, taken out, and cooled to room temperature to obtain a mica board.

[0072] Comparative Example 3

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

[0074] The commercially available SH-9502 silicone resin with a solid content of 50% was evenly coated on a 160g / cm 2 The mica paper is coated with glue at an average amount of 3%, and the solvent is removed in a drying oven at 125°C for 2 minutes to obtain the coated mica paper. Then 20 layers of the coated mica paper are stacked in the same direction, put into a flat vulcanizer, pressed at 220°C and 30MPa for 90 minutes, taken out, and cooled to room temperature to obtain a mica board.

[0075] Comparative Example 4

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

[0077] The commercially available SH-9502 silicone resin with a solid content of 50% was evenly coated on a 160g / cm 2The mica paper is coated with glue at an average amount of 3%, and the solvent is removed in a 125°C oven for 2 minutes to obtain the coated mica paper. Then 20 layers of the coated mica paper are stacked in the same direction, put into a flat vulcanizer, pressed at 220°C and 30MPa for 180 minutes, taken out, and cooled to room temperature to obtain a mica board.

[0078] Comparative Example 5

[0079] This comparative example provides a silicone resin composition, in parts by weight, the preparation raw materials include 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrogensilane, 15 parts of 3-glycidyloxypropyltrimethoxysilane, 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 (the effective content of platinum is 3000ppm).

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

[0081] (1) Preparation of silicone resin adhesive: adding a formula amount of methyltrimethoxysilane, vinyltrimethoxysilane, trimethoxyhydrogensilane, 3-glycidyloxypropyltrimethoxysilane, ethanol, deionized water, and catalyst HND-33 into a reaction kettle and reacting at 70° C. for 4 hours, then removing the catalyst HND-33 by filtration, and finally treating under vacuum conditions for 2.5 hours to obtain a silicone resin adhesive;

[0082] (2) Preparation of a silicone resin composition: Stir and mix silicone resin base glue, 1-ethynylcyclohexanol, ethyl acetate, and platinum catalyst at room temperature to obtain a silicone resin composition.

[0083] The specific application of the silicone resin composition in the preparation of the 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 is prepared by raw materials including, by weight, 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrogensilane, 15 parts of 3-glycidyloxypropyltrimethoxysilane, 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 (the effective content of platinum is 3000 ppm).

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

[0087] The specific application of the silicone resin composition in the preparation of the 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 is prepared by raw materials including, by weight, 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrogensilane, 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 (the effective content of platinum is 3000 ppm).

[0090] The preparation method of the silicone resin composition of this comparative example comprises:

[0091] (1) Preparation of silicone resin adhesive: adding a formula amount of methyltrimethoxysilane, vinyltrimethoxysilane, trimethoxyhydrogensilane, ethanol, deionized water, and catalyst HND-33 into a reaction kettle and reacting at 70° C. for 4 hours, then removing the catalyst HND-33 by filtration, and finally treating under vacuum conditions for 2.5 hours to obtain a silicone resin adhesive;

[0092] (2) Preparation of silicone resin composition: silicone resin base glue and n-butyl titanate are placed in a reaction kettle and reacted at 130° C. for 3 h, cooled to 70° C. and degased under vacuum conditions until no obvious liquid is distilled out, cooled to room temperature, 1-ethynylcyclohexanol, ethyl acetate, and platinum catalyst are added in sequence, stirred and mixed to obtain a silicone resin composition.

[0093] The specific application of the silicone resin composition in the preparation of the 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 is prepared by raw materials including, by weight, 80 parts of methyltrimethoxysilane, 9 parts of vinyltrimethoxysilane, 15 parts of trimethoxyhydrogensilane, 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 (the effective content of platinum is 3000 ppm).

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

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

[0098] The mica boards of the above-mentioned Examples 1 to 6 and Comparative Examples 1 to 8 were cut into 2 cm×2 cm small pieces, and the delamination of the mica boards during the cutting process was observed. Then, 5 pieces of the cut mica boards were taken from each group, and boiled in boiling water for 30 minutes to observe the delamination. The test results are shown in Table 1:

[0099] Table 1 Performance test results of the silicone resin compositions of Examples 1 to 6 and Comparative Examples 1 to 8 applied in the preparation of mica boards.

[0100]

[0101]

[0102] Specifically, as shown in the test results of Table 1, it can be seen from the comparison between Examples 1 to 5 and Comparative Examples 1 to 4 that the silicone resin composition prepared by the present invention can be applied to the production of mica boards to make the mica boards have better water boiling resistance. It can be seen from Comparative Examples 1 to 4 that when commercially available silicone resin is used, the solvent drying temperature is increased to 125°C, the pressing temperature is increased to 220°C, and the pressing time is increased to 180 minutes, so that the cut mica boards will not be delaminated. However, in the water boiling resistance test, 20% of the mica boards still have delamination. Therefore, in the production of mica boards, the silicone resin composition of the present invention has a shorter pressing time and a lower pressing temperature than the existing silicone resins on the market, and the mica boards have better high-temperature water boiling resistance and delamination performance.

[0103] By comparing Example 1 with Comparative Example 5, it can be seen that due to the lack of n-butyl titanate, 20% of the mica boards showed delamination during the water boiling resistance test, indicating that the lack of n-butyl titanate weakens the bonding strength between the silicone resin composition of the present invention and the mica paper, thereby affecting its high temperature water boiling resistance.

[0104] By comparing Example 1 with Comparative Example 6, it can be seen that when n-butyl titanate is replaced by isopropyl titanate, 20% of the mica plates are delaminated, indicating that n-butyl titanate makes the bonding strength of the silicone resin composition of the present invention to mica paper better than that of isopropyl titanate, and thus its high temperature boiling resistance is also better than that of isopropyl titanate.

[0105] By comparing Example 1 with Comparative Example 7, it can be seen that when 3-glycidyloxypropyltrimethoxysilane is missing, 20% of the mica boards are delaminated, indicating that the lack of 3-glycidyloxypropyltrimethoxysilane weakens the bonding strength between the silicone resin composition of the present invention and the mica paper, thereby affecting its performance.

[0106] By comparing Example 1 with Comparative Example 8, it can be seen that when 3-glycidyloxypropyltrimethoxysilane is replaced by γ-aminopropyltrimethoxysilane, 30% of the mica boards are delaminated, indicating that the improvement of the boiling resistance of mica boards by γ-aminopropyltrimethoxysilane is significantly inferior to that of 3-glycidyloxypropyltrimethoxysilane.

[0107] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, it is not limited to those listed in the embodiments. Those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A silicone resin composition, characterized in that: The raw materials for preparation include, by weight, 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-glycidyloxypropyltrimethoxysilane, 30 to 50 parts of a compatibilizer, 40 to 70 parts of deionized water, 5 to 20 parts of n-butyl titanate, 3 to 10 parts of a catalyst, 0.02 to 0.7 parts of a platinum catalyst, 0.006 to 0.1 parts of an inhibitor and 50 to 100 parts of a 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 trialkoxyhydrogensilane is selected from at least one of trimethoxyhydrogensilane and triethoxyhydrogensilane.

3. The silicone resin composition according to claim 1, characterized in that The solid acid catalyst has an acid capacity of ≥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 of ​​≥20 m 2 / g.

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

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 acetylenic alcohol compounds, maleic acid esters, fumaric acid esters and tetramethyltetravinylcyclotetrasiloxane.

7. The silicone resin composition according to claim 1, characterized in that: The diluent is selected from at least one of alcohol compounds, benzene compounds and ester compounds.

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) Preparing a silicone resin adhesive: adding the methyltrialkoxysilane, the vinyltrialkoxysilane, the trialkoxyhydrogensilane, the 3-glycidyloxypropyltrimethoxysilane, the compatibilizer, the deionized water, and the catalyst in a formula amount into a reaction kettle and reacting at 65° C. to 75° C. for 3 h to 5 h, then filtering to remove the catalyst, and finally treating under vacuum conditions for 1.5 h to 3 h to obtain a silicone resin adhesive; (2) Preparation of a silicone resin composition: The silicone resin base glue and the n-butyl titanate are placed in a reaction kettle and reacted at 110° C. to 150° C. for 3 h to 5 h, then cooled to 60° C. to 80° C. and degassed under vacuum until no obvious liquid is distilled out, then cooled to room temperature, the inhibitor, the diluent, and the platinum catalyst are added, stirred and mixed to obtain a silicone resin composition.

10. Use of the silicone resin composition according to any one of claims 1 to 8 or the silicone resin composition prepared by the method for preparing the silicone resin composition according to claim 9 in the preparation of mica boards.

Images