A high-resilience one-component organopolysiloxane composition and its preparation method

Abstract

The purpose of this invention is to provide a high-resilience single-component organopolysiloxane composition and its preparation method, suitable for sealing and bonding of various automotive, industrial, and electronic components, especially for sealing and bonding applications of in-situ molded gaskets (CIPG). The high-resilience single-component organopolysiloxane composition of this invention comprises at least the following components (A)-(E): (A) an organopolysiloxane having at least two alkenyl groups per molecule; (B) an organopolysiloxane having at least two Si-H bonds per molecule; (C) a hyperbranched organosilicon crosslinking agent; (D) a hydrosilylation catalyst; and (E) fumed silica. This invention uses multifunctional organosilicon molecules as the core basis of the hyperbranched structure and prepares the hyperbranched organosilicon crosslinking agent through a hydrosilylation reaction. On the one hand, the hyperbranched structure increases the spatial distance between crosslinking points, which enables the cured polysiloxane composition to have good resilience. On the other hand, active groups that increase interfacial adhesion are introduced into this hyperbranched organosilicon crosslinking agent, which not only play a role in crosslinking and curing, but also have good adhesion performance to the material interface.

Description

Technical Field

[0001] This invention relates to a high-resilience single-component organopolysiloxane composition and its preparation method, belonging to the field of thermosetting, adhesive sealing, and in-situ molded gasket (CIPG) solutions. Background Technology

[0002] Organosilicon materials have gained widespread attention and application in various industries due to their excellent heat resistance, cold resistance, dielectric properties, ozone resistance and atmospheric aging resistance, as well as their wide operating temperature range, from -60℃ (or lower) to +250℃ (or higher).

[0003] In response to the precision, airtightness, and integration requirements of the current new energy vehicle industry, the design of novel automotive sealing connectors for automotive motors, electronic controls, oil pump controllers, and EHPS steering pumps is trending towards larger sizes and more complex structures. This paper proposes an automotive connector sealing technology based on CIPG (Compound Injection Processing). This sealing product also possesses performance requirements for high temperature resistance, low temperature resistance, high pressure resistance, and high humidity resistance, representing a mainstream direction for the future development and application of automotive sealing connectors.

[0004] This invention aims to provide a single-component organopolysiloxane composition with high resilience after curing and its preparation method, suitable for sealing and bonding of various automotive, industrial, and electronic components, especially for sealing and bonding applications of in-situ molded gaskets (CIPG). On one hand, by designing the molecular structure of the hyperbranched organosilicon crosslinking agent, the spatial distance between crosslinking points can be increased, resulting in excellent resilience of the cured polysiloxane composition. On the other hand, active groups that enhance interfacial adhesion are introduced into this hyperbranched organosilicon crosslinking agent, providing both crosslinking and curing effects while also exhibiting excellent adhesion to the material interface. Summary of the Invention

[0005] The purpose of this invention is to provide a single-component organopolysiloxane composition with high resilience after curing and its preparation method, suitable for sealing and bonding of various automotive, industrial, and electronic components, especially for sealing and bonding applications of in-situ molded gaskets (CIPG). This invention uses multifunctional organosilicon molecules as the core basis of a hyperbranched structure and prepares a hyperbranched organosilicon crosslinking agent through a hydrosilylation reaction. This crosslinking agent is both a multifunctional active crosslinking agent capable of participating in the hydrosilylation reaction and contains active groups that can increase interfacial adhesion. On the one hand, the design of the hyperbranched organosilicon crosslinking agent molecular structure can increase the spatial distance between crosslinking points, resulting in excellent resilience of the cured polysiloxane composition; on the other hand, the introduction of active groups that increase interfacial adhesion into this hyperbranched organosilicon crosslinking agent not only performs crosslinking and curing but also provides excellent adhesion to the material interface.

[0006] A high-resilience one-component organopolysiloxane composition of the present invention comprises at least the following components (A)-(E): (A) 5-80 parts of organopolysiloxanes having at least 2 alkenyl groups per molecule; (B) 0-10 parts of organopolysiloxanes with at least 2 Si-H bonds per molecule; (C) 0-60 parts of hyperbranched organosilicon crosslinking agent; (D) 0-1 parts of hydrogenation silylation catalyst; (E) Fumed silica 10-40 parts; Component (A) is an organopolysiloxane with at least two alkenyl groups per molecule, and its general structural formula is (R 1 R 2 2SiO 1 / 2 (R) 1 R 2 SiO 2 / 2 ) a (R) 2 SiO 3 / 2 ) b (SiO) 4 / 2 ) c , where R 1 R 2 Each group independently represents an unsubstituted or substituted monovalent hydrocarbon group. Preferably, the monovalent hydrocarbon group has 1 to 10 carbon atoms, particularly 1 to 6, and examples include: lower alkyl groups such as methyl, ethyl, propyl, and isopropyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl; alkane groups containing dilute bonds such as vinyl and propenyl; or groups obtained by substituting some or all of the hydrogen atoms of the above groups with halogen atoms, cyano groups, etc., such as chloromethyl and cyanoethyl. More preferably, groups derived from methyl, ethyl, vinyl, phenyl, etc., and R... 1 and R 2 At least one group is vinyl; a = 0~500 (excluding 0), b = 0~2, c = 0~2, a+b+c = 1~500.

[0007] Component (B) is an organopolysiloxane with at least two Si-H bonds per molecule, and its general structural formula is (R 3 R 4 2SiO 1 / 2 (R) 3 R 4 SiO 2 / 2 ) m (R) 5 SiO 3 / 2 ) n (SiO) 4 / 2 ) x, where R 3 R 4 R 5 Each group independently represents an unsubstituted or substituted monovalent hydrocarbon group. Preferably, the monovalent hydrocarbon group has 1 to 10 carbon atoms, particularly 1 to 6. Examples include: lower alkyl groups such as methyl, ethyl, propyl, and isopropyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl; alkane groups containing dilute bonds such as vinyl and propenyl; or groups obtained by substituting some or all of the hydrogen atoms of the above groups with halogen atoms, cyano groups, etc., such as chloromethyl and cyanoethyl. More preferably, groups derived from methyl, ethyl, phenyl, etc., and R... 3 R 4 and R 5 At least one group is a hydrogen atom; m=0~100, n=0~3, x=0~2, m+n+x=0.5~100.

[0008] The chemical structural formula of the hyperbranched organosilicon crosslinking agent (C) can be represented as follows:

[0009] Where y = integers from 0 to 5, the maximum value of y should not exceed 5. If it exceeds 5, on the one hand, the number of reaction steps is too large, resulting in low efficiency, and on the other hand, the chain segment is too long, which has no substantial meaning for improving the rebound.

[0010] The core can be one of 1,3,5,7-tetramethylcyclotetrasiloxane, tetraepoxycyclohexylethyl 2,4,6,8-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, pentamethylpentvinylcyclopentasiloxane, tetramethyltetravinylcyclotetrasiloxane, octavinyl-POSS, side-vinyl silicone oil, side-hydrogen-containing silicone oil, end-side vinyl silicone oil, and end-side hydrogen-containing silicone oil. In this invention, the side-vinyl silicone oil, side-hydrogen-containing silicone oil, end-side vinyl silicone oil, and end-side hydrogen-containing silicone oil specifically refer to silicone oils with ≥3 vinyl or Si-H groups per molecule.

[0011] The preparation method of the hyperbranched organosilicon crosslinking agent of component (C) is as follows: When the active functional group of the core is vinyl: ① Dilute a certain amount of the raw material representing the core with toluene 1-3 times, then add a certain proportion of platinum catalyst, mix well and set aside; ② Add a certain amount of 1,1,3,3-tetramethyldisiloxane to a reaction flask, dilute with toluene 1-3 times, stir well and heat to 40-60℃, then slowly add the mixture obtained in the previous step, controlling the reaction temperature <70℃, and after the addition is complete, keep the reaction at this temperature for 2 hours; ③ Add a certain amount of tetramethyldivinyldisiloxane to a reaction flask, dilute with toluene 1-3 times, stir well and heat to 40-60℃, then slowly add the mixture obtained in the previous step. The compound is slowly added dropwise, and the reaction temperature is controlled below 70℃. After the addition is complete, the reaction is kept at this temperature for 2 hours. Steps ② and ③ are repeated until the target y value is obtained. When y = 0 and 1, only ①→② is performed, and ③ is not required. When y = 2 and 3, ①→②→③→② is required. When y = 4 and 5, ①→②→③→②→③→② is required. After the repeated reaction is completed, a certain amount of end-capping agent heated to 40-60℃ is diluted 1-3 times with toluene and the mixture obtained in the first step is slowly added dropwise. After the addition is complete, the temperature is raised to 90-100℃ and the reaction is kept at this temperature for 4 hours. The reaction is then terminated. The solvent is removed by vacuum distillation to obtain (C) hyperbranched organosilicon crosslinking agent. When the active functional group of the core is Si-H, the mixing of the platinum catalyst is carried out in step ③; after the reaction in step ①, step ③ is carried out first, followed by step ②, until the target y value is obtained; when y=1 and 2, ①→③→② is required; when y=3 and 4, ①→③→②→③→② is required; when y=5, ①→③→②→③→②→③ is required; after the repeated reaction is completed, a certain amount of the end-capping agent toluene dilution mixture heated to 40-60℃ is slowly added dropwise to the mixture obtained in step 1. After the addition is completed, the temperature is raised to 90-100℃, and the reaction is stopped after 4 hours of holding at the temperature; the solvent is removed by vacuum distillation to obtain (C) hyperbranched organosilicon crosslinking agent; When octavinyl-POSS is selected as the core, the amount of toluene added is more than 10 times that of octavinyl-POSS; during the repeated ② or ③ reaction process, the amount of raw materials added is 1:1 in the ratio of vinyl to Si-H; in the final step ④, the amount of end-capping agent added is 1~1.2:1 in the ratio of vinyl to Si-H. The amount of platinum catalyst added is 5-50 ppm of the total weight of all raw materials participating in the reaction except toluene; the end-capping agent is one or more of tetramethyldivinyldisiloxane, 1,2-epoxy-4-vinylcyclohexane, allyl glycidyl ether, n-butyl acrylate, and 3-(methacryloyloxy)propyltrimethoxysilane.

[0012] The component (D) hydrogenation silylation catalyst can be selected from platinum-based, rhodium-based, or palladium-based catalysts, with platinum-based catalysts preferred considering catalytic activity. Platinum-based catalysts can be one or a mixture of several of the following: platinum chloride, alcohol-modified platinum chloride, platinum chloride and diene complexes, platinum-olefin complexes, platinum-carbonyl complexes such as platinum bis(acetoacetate) or platinum bis(acetylacetone), platinum chloride-alkenylsiloxane complexes such as platinum chloride-divinyltetramethyldisiloxane complex or platinum chloride-tetravinyltetramethylcyclotetrasiloxane, platinum-alkenylsiloxane complexes such as platinum-divinyltetramethyldisiloxane complex or platinum-tetravinyltetramethylcyclotetrasiloxane, platinum chloride and ethynyl alcohol complexes, and encapsulated platinum catalysts.

[0013] The component (E) fumed silica is preferably fumed silica treated with a treatment agent, which may be one or a mixture of several of the following: trimethylchlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, methyltrichlorosilane, trimethylethoxysilane, vinyltrimethoxysilane, γ-aminopropyltriethoxysilane, methyl silicone oil, ethyl silicone oil, toluene silicone oil, methyl hydrogen silicone oil, ethyl hydrogen silicone oil, hydroxyl silicone oil, hexamethyldisilazane, etc.

[0014] Based on this patented invention, adjustments can be made to meet specific application requirements: for example, adding fluorescent agents, carbon black, pigments, titanium dioxide, etc., to adjust the appearance and detection functions; adding silica powder, etc., for reinforcement; adding alumina, zinc oxide, magnesium oxide, aluminum hydroxide, etc., to improve thermal conductivity and flame retardancy; adding inhibitors, etc., to adjust the shelf life and working time, etc. Alternatively, the interaction between the silicone oil or resin matrix and the fumed silica can be enhanced through common high-temperature treatment methods to improve the reinforcement effect. This invention provides a single-component organopolysiloxane composition with high resilience after curing and its preparation method, suitable for sealing and bonding of various automotive, industrial, and electronic components, especially for sealing and bonding scenarios in in-situ molded gasket (CIPG) applications. The beneficial effects of this invention are: ① Using multifunctional organosilicon molecules as the core basis of a hyperbranched structure, a hyperbranched organosilicon crosslinking agent is prepared through a hydrosilylation reaction. The design of the hyperbranched organosilicon crosslinking agent molecular structure increases the spatial distance between crosslinking points, resulting in a polysiloxane composition with excellent resilience after curing, facilitating the rework of automotive, industrial, and electronic components; ② Traditional formulations often use silane coupling agents to improve the adhesion performance of materials to the bonding interface. However, silane coupling agents often lack or only have one hydrosilylation reactive group, thus reducing the bulk strength while improving adhesion performance. The hyperbranched organosilicon crosslinking agent of the present invention is a multifunctional active crosslinking agent that can participate in hydrosilylation reaction, and also contains active groups that can increase interfacial adhesion, thus achieving a three-in-one effect of not reducing bulk strength, enhancing resilience and improving adhesion performance. Implementation

[0015] The following specific embodiments describe the principles and features of the present invention. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0016] Example 1: Preparation of hyperbranched organosilicon crosslinking agent C-1: 500g of end-side vinyl silicone oil (vinyl content 0.5wt%, molecular weight 60,000) was diluted 3 times with toluene, and then 0.015g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) was added and mixed thoroughly. 12.5g of 1,1,3,3-tetramethyldisiloxane was added to a reaction flask and diluted 1 part with toluene. The mixture was stirred thoroughly and heated to 40°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours.

[0017] 3.75 g of vinyltrimethoxysilane was diluted 1:1 with toluene, heated to 50 °C, and the mixture obtained in the previous step was slowly added dropwise. After the addition was complete, the temperature was raised to 90 °C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-1 with a hydrogen content of 0.13 mmol / g.

[0018] Example 2: Preparation of hyperbranched organosilicon crosslinking agent C-2 500g of octavinyl-POSS was diluted 12 times with toluene, and then 0.1g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) was added and mixed thoroughly. 848.7g of 1,1,3,3-tetramethyldisiloxane was added to a reaction flask and diluted 2 times with toluene. The mixture was stirred thoroughly and heated to 60°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours.

[0019] 117.1 g of vinyltrimethoxysilane, 90.17 g of allyl glycidyl ether, and 392.4 g of 3-(methacryloyloxy)propyltrimethoxysilane were mixed thoroughly and diluted with toluene by an octet. The mixture was heated to 50 °C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 100 °C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-2 with a hydrogen content of 1.62 mmol / g.

[0020] Example 3: Preparation of hyperbranched organosilicon crosslinking agent C-3 Dilute 50g of hydrogen-containing silicone oil (0.9wt% hydrogen content, molecular weight 2000) with toluene by half and set aside. Add 83.9g of tetramethyldivinyldisiloxane to a reaction flask, then add 0.03g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%), mix thoroughly, and dilute with toluene by half. Stir until homogeneous and heat to 50°C. Then slowly add the mixture obtained in the previous step dropwise, controlling the reaction temperature <70°C. After the addition is complete, maintain the temperature for 2 hours. Add 60.4g of 1,1,3,3-tetramethyldisiloxane to a reaction flask, dilute with toluene by half, stir until homogeneous, and heat to 50°C. Then slowly add the mixture obtained in the previous step dropwise, controlling the reaction temperature <70°C. After the addition is complete, maintain the temperature for 2 hours.

[0021] 5.7 g of allyl glycidyl ether, 6,4-butyl acrylate, 12.4 g of 3-(methacryloyloxy)propyltrimethoxysilane, and 67.1 g of tetramethyldivinyldisiloxane were mixed thoroughly and diluted with toluene by an octet. The mixture was heated to 50 °C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 100 °C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-3 with a vinyl content of 1.05 mmol / g.

[0022] Example 4: Preparation of hyperbranched organosilicon crosslinking agent C-4 500g of end-side vinyl silicone oil (vinyl content 0.7wt%, molecular weight 20,000) was diluted twice with toluene, and then 0.14g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) was added and mixed thoroughly. 17.5g of 1,1,3,3-tetramethyldisiloxane was added to a reaction flask and diluted twice with toluene. The mixture was stirred thoroughly and heated to 40°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 24.2g of tetramethyldivinyldisiloxane was added to a reaction flask and diluted twice with toluene. The mixture was stirred thoroughly and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 17.5 g of 1,1,3,3-tetramethyldisiloxane was added to the reaction flask and diluted with toluene by 1:1. The mixture was stirred until homogeneous and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, with the reaction temperature controlled below 70°C. After the addition was complete, the mixture was kept at this temperature for 2 hours.

[0023] 3.23 g of 1,2-epoxy-4-vinylcyclohexane, 7.7 g of vinyltrimethoxysilane, and 10.5 g of tetramethyldivinyldisiloxane were mixed thoroughly and diluted with toluene by an octet. The mixture was heated to 50 °C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 100 °C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain the hyperbranched organosilicon crosslinking agent C-4, with a vinyl content of 0.09 mmol / g.

[0024] Example 5: Preparation of hyperbranched organosilicon crosslinking agent C-5 240.5 g of 1,3,5,7-tetramethylcyclotetrasiloxane was diluted 1 part with toluene and set aside. 186.4 g of tetramethyldivinyldisiloxane was added to a reaction flask, followed by 0.06 g of a platinum-divinyltetramethyldisiloxane complex (Pt 20wt%). The mixture was thoroughly mixed and diluted 1 part with toluene. The mixture was stirred until homogeneous and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 134.32 g of 1,1,3,3-tetramethyldisiloxane was added to a reaction flask and diluted 1 part with toluene. The mixture was stirred until homogeneous and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. Add 186.4 g of tetramethyldisiloxane to a reaction flask, dilute it with toluene by half, stir well, and heat to 50°C. Then, slowly add the mixture obtained in the previous step dropwise, controlling the reaction temperature to be <70°C. After the addition is complete, maintain the temperature for 2 hours. Add 134.32 g of 1,1,3,3-tetramethyldisiloxane to a reaction flask, dilute it with toluene by half, stir well, and heat to 50°C. Then, slowly add the mixture obtained in the previous step dropwise, controlling the reaction temperature to be <70°C. After the addition is complete, maintain the temperature for 2 hours.

[0025] 114.14 g of allyl glycidyl ether and 148.23 g of vinyltrimethoxysilane were mixed thoroughly and diluted with toluene by an octet. The mixture was heated to 50 °C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 90 °C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain the hyperbranched organosilicon crosslinking agent C-5, which has a hydrogen content of 1.75 mmol / g.

[0026] Example 6: Preparation of hyperbranched organosilicon crosslinking agent C-6 344.66 g of tetramethyltetravinylcyclotetrasiloxane was diluted 1 / 2 with toluene, and then 0.07 g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) was added and mixed thoroughly. 134.32 g of 1,1,3,3-tetramethyldisiloxane was added to a reaction flask and diluted 1 / 2 with toluene. The mixture was stirred thoroughly and heated to 40°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 186.4 g of tetramethyldivinyldisiloxane was added to a reaction flask and diluted 1 / 2 with toluene. The mixture was stirred thoroughly and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. Add 134.32 g of 1,1,3,3-tetramethyldisiloxane to a reaction flask, dilute with toluene by half, stir well, and heat to 50°C. Then, slowly add the mixture obtained in the previous step dropwise, controlling the reaction temperature to be <70°C. After the addition is complete, maintain the reaction temperature for 2 hours. Add 186.4 g of tetramethyldivinyldisiloxane to a reaction flask, dilute with toluene by half, stir well, and heat to 50°C. Then, slowly add the mixture obtained in the previous step dropwise, controlling the reaction temperature to be <70°C. After the addition is complete, maintain the reaction temperature for 2 hours. Add 134.32 g of 1,1,3,3-tetramethyldisiloxane to a reaction flask, dilute with toluene by half, stir well, and heat to 50°C. Then, slowly add the mixture obtained in the previous step dropwise, controlling the reaction temperature to be <70°C. After the addition is complete, maintain the reaction temperature for 2 hours.

[0027] 248.35 g of 3-(methacryloyloxy)propyltrimethoxysilane was diluted 1:1 with toluene, heated to 50 °C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 100 °C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain the hyperbranched organosilicon crosslinking agent C-6, which has a hydrogen content of 2.19 mmol / g.

[0028] The components of the high-resilience single-component organopolysiloxane compositions in Examples 7-10 and Comparative Examples 1-3 are described below, and the specific formulation composition is shown in Table 1.

[0029] Organopolysiloxane A-1, which has at least two alkenyl groups per molecule: (CH2=CH(CH3)2SiO 1 / 2 (CH3)2SiO 2 / 2 ) 400 Organopolysiloxane A-2, which has at least two alkenyl groups per molecule: (CH2=CH(CH3)2SiO 1 / 2 ) 0.2 (CH3)3SiO 1 / 2 )0.8 (SiO) 4 / 2 ) 1.25 Organopolysiloxane B-1, which has at least two Si-H bonds per molecule: ((CH3)3SiO 1 / 2 (CH3)HSiO 2 / 2 ) 30 (CH3)2SiO 2 / 2 ) 50 Organopolysiloxane B-2, which has at least two Si-H bonds per molecule: ((CH3)2HSiO 1 / 2 (SiO) 4 / 2 ) 0.8 Hydrogenation silylation catalyst D-1: Platinum-divinyltetramethyldisiloxane complex diluted with dimethicone oil, Pt content 5000 ppm Hydrosilylation catalyst D-2: Encapsulated platinum catalyst with 5000 ppm Pt content Fumed silica E-1; Fumed silica treated with hexamethyldisilazane Fumed silica E-2; methyl silicone oil treated fumed silica The test items and test conditions are as follows: Thermosetting conditions: Examples 7-10 and Comparative Examples 1-3 were all cured at 150℃ for 30 min; Adhesion test: The material is cast aluminum VS cast aluminum. The adhesion judgment method is whether the interface is easy to peel off and can be torn off in strips. If the interface is not easy to peel off and it is difficult to tear off in strips, then the adhesion is OK. If the interface is easy to peel off and can be torn off in strips, then the adhesion is NG. Permanent compression loss test: The adhesive strip was applied at a height of 2.0 ± 0.2 mm and cured at 150℃ for 30 minutes. The cured strip height was then measured as h0. The strip was then compressed to 40% and secured with screws. Afterward, it was aged at 125℃ for 7 days. Following aging, the strip was removed, the screws and pressure were released, and it was left at room temperature for 4 hours. The final strip height h1 was then measured. The permanent compression loss rate was calculated as (h0 - h1) / h0. Table 1. Formulation composition and performance of Examples 7-10 and Comparative Examples 1-3

[0030] As can be seen from the test results in Table 1, compared with Comparative Examples 1-2, the hyperbranched organosilicon crosslinking agent of the present invention has a more significant effect on improving compression resilience (permanent compression loss rate %) in Examples 7-10, and also has a better adhesion effect on the bonding interface. Furthermore, the results of Comparative Examples 2 and 1 show that the addition of conventional coupling agents has a negative impact on compression resilience. Introducing groups that promote the bonding interface into the hyperbranched organosilicon crosslinking agent successfully avoids the negative impact of conventional coupling agents on compression resilience.

Claims

1. A high-resilience one-component organopolysiloxane composition, characterized in that, It consists of the following components in parts by mass: Organopolysiloxane A-1, having at least two alkenyl groups per molecule: 60 parts; Organopolysiloxane A-2, having at least two alkenyl groups per molecule: 20 parts; Organopolysiloxane B-1 with at least 2 Si-H bonds per molecule: 1 part; Organopolysiloxane B-2 with at least 2 Si-H bonds per molecule: 2 parts; Hyperbranched organosilicon crosslinking agent C-1: 1.5 parts; Hyperbranched organosilicon crosslinking agent C-2: 5.5 parts; Hydrosilylation catalyst D-2: 0.1 parts; Fumed silica E-1: 10 parts; Methylbutynol: 0.05 parts; The A-1 is (CH2=CH(CH3)2SiO) 1 / 2 (CH3)2SiO 2 / 2 ) 400 ; The A-2 is (CH2=CH(CH3)2SiO) 1 / 2 ) 0.2 (CH3)3SiO 1 / 2 ) 0.8 (SiO) 4 / 2 ) 1.25 ; The B-1 is (CH3)3SiO 1 / 2 (CH3)HSiO 2 / 2 ) 30 (CH3)2SiO 2 / 2 ) 50 ; The B-2 is ((CH3)2HSiO 1 / 2 (SiO) 4 / 2 ) 0.8 ; The D-2 is a capsule-type platinum catalyst with a Pt content of 5000 ppm; E-1 is fumed silica treated with hexamethyldisilazane; The C-1 was prepared by the following steps: 500g of end-side vinyl silicone oil, with a vinyl content of 0.5wt% and a molecular weight of 60,000, was diluted 3 times with toluene, and then 0.015g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) was added and mixed evenly for later use; 12.5g of 1,1,3,3-tetramethyldisiloxane was added to a reaction flask and diluted 1 times with toluene, stirred evenly, and heated to 40°C. The mixture obtained in the previous step was then slowly added dropwise, controlling the reaction temperature to be <70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours; 3.75g of vinyltrimethoxysilane was diluted 1 times with toluene, heated to 50°C, and the mixture obtained in the previous step was slowly added dropwise. After the addition was complete, the temperature was raised to 90°C, and the reaction was maintained at this temperature for 4 hours, after which the reaction was terminated; the solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-1 with a hydrogen content of 0.13mmol / g; The C-2 is prepared by the following steps: 500g of octavinyl-POSS is diluted 12 times with toluene, then 0.1g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) is added and mixed thoroughly. 848.7g of 1,1,3,3-tetramethyldisiloxane is added to a reaction flask and diluted 2 times with toluene. The mixture is stirred thoroughly and heated to 60°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to be <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours. 117.1g of vinyltrimethoxysilane, 90.17g of allyl glycidyl ether, and 392.4g of... 3-(methacryloyloxy)propyltrimethoxysilane was mixed evenly, diluted with toluene by 1:1, heated to 50°C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 100°C, and the reaction was stopped after 4 hours. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-2 with a hydrogen content of 1.62 mmol / g.

2. A high-resilience one-component organopolysiloxane composition, characterized in that, It consists of the following components in parts by weight: Organopolysiloxane A-1, having at least two alkenyl groups per molecule: 40 parts; Organopolysiloxane A-2, having at least two alkenyl groups per molecule: 20 parts; Organopolysiloxane B-1 with at least 2 Si-H bonds per molecule: 2 parts; Organopolysiloxane B-2 with at least 2 Si-H bonds per molecule: 2 parts; Hyperbranched organosilicon crosslinking agent C-1: 4 parts; Hyperbranched organosilicon crosslinking agent C-5: 1.5 parts; Hydrosilylation catalyst D-2: 1 part; Fumed silica E-1: 20 parts; Methylbutynol: 0.5 parts; The A-1 is (CH2=CH(CH3)2SiO) 1 / 2 (CH3)2SiO 2 / 2 ) 400 ; The A-2 is (CH2=CH(CH3)2SiO) 1 / 2 ) 0.2 (CH3)3SiO 1 / 2 ) 0.8 (SiO) 4 / 2 ) 1.25 ; The B-1 is (CH3)3SiO 1 / 2 (CH3)HSiO 2 / 2 ) 30 (CH3)2SiO 2 / 2 ) 50 ; The B-2 is ((CH3)2HSiO 1 / 2 (SiO) 4 / 2 ) 0.8 ; The D-2 is a capsule-type platinum catalyst with a Pt content of 5000 ppm; E-1 is fumed silica treated with hexamethyldisilazane; The C-1 was prepared by the following steps: 500g of end-side vinyl silicone oil, with a vinyl content of 0.5wt% and a molecular weight of 60,000, was diluted 3 times with toluene, and then 0.015g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) was added and mixed evenly for later use; 12.5g of 1,1,3,3-tetramethyldisiloxane was added to a reaction flask and diluted 1 times with toluene, stirred evenly, and heated to 40°C. The mixture obtained in the previous step was then slowly added dropwise, controlling the reaction temperature to be <70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours; 3.75g of vinyltrimethoxysilane was diluted 1 times with toluene, heated to 50°C, and the mixture obtained in the previous step was slowly added dropwise. After the addition was complete, the temperature was raised to 90°C, and the reaction was maintained at this temperature for 4 hours, after which the reaction was terminated; the solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-1 with a hydrogen content of 0.13mmol / g; The C-5 was prepared by the following steps: 240.5 g of 1,3,5,7-tetramethylcyclotetrasiloxane was diluted 1 part with toluene and set aside; 186.4 g of tetramethyldivinyldisiloxane was added to a reaction flask, followed by 0.06 g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%), which was mixed thoroughly and diluted 1 part with toluene. The mixture was stirred until homogeneous and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 134.32 g of the C-5 was then added. 1,1,3,3-Tetramethyldisiloxane was added to a reaction flask and diluted 1:1 with toluene. The mixture was stirred thoroughly and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. Then, 186.4 g of tetramethyldivinyldisiloxane was added to the reaction flask and diluted 1:1 with toluene. The mixture was stirred thoroughly and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. Finally, 134.32 g of... 1,1,3,3-Tetramethyldisiloxane was added to a reaction flask and diluted with toluene by 1:

1. The mixture was stirred until homogeneous and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, with the reaction temperature controlled below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 114.14 g of allyl glycidyl ether and 148.23 g of vinyltrimethoxysilane were then mixed until homogeneous and diluted with toluene by 1:

1. The mixture was heated to 50°C and slowly added dropwise. After the addition was complete, the temperature was raised to 90°C and the reaction was maintained at this temperature for 4 hours. The reaction was then terminated, and the solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-5 with a hydrogen content of 1.75 mmol / g.

3. A high-resilience one-component organopolysiloxane composition, characterized in that, It consists of the following components in parts by weight: Organopolysiloxane A-1, having at least two alkenyl groups per molecule: 20 parts; Organopolysiloxane A-2, having at least two alkenyl groups per molecule: 10 parts; Organopolysiloxane B-1 with at least 2 Si-H bonds per molecule: 2 parts; Hyperbranched organosilicon crosslinking agent C-2: 2 parts; Hyperbranched organosilicon crosslinking agent C-3: 1 part; Hyperbranched organosilicon crosslinking agent C-4: 10 parts; Hyperbranched organosilicon crosslinking agent C-6: 2 parts; Hydrosilylation catalyst D-2: 0.5 parts; Fumed silica E-2: 30 parts; The A-1 is (CH2=CH(CH3)2SiO) 1 / 2 (CH3)2SiO 2 / 2 ) 400 ; The A-2 is (CH2=CH(CH3)2SiO) 1 / 2 ) 0.2 (CH3)3SiO 1 / 2 ) 0.8 (SiO) 4 / 2 ) 1.25 ; The B-1 is (CH3)3SiO 1 / 2 (CH3)HSiO 2 / 2 ) 30 (CH3)2SiO 2 / 2 ) 50 ; The D-2 is a capsule-type platinum catalyst with a Pt content of 5000 ppm; E-2 is fumed silica treated with methyl silicone oil. The C-2 is prepared by the following steps: 500g of octavinyl-POSS is diluted 12 times with toluene, then 0.1g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) is added and mixed thoroughly. 848.7g of 1,1,3,3-tetramethyldisiloxane is added to a reaction flask and diluted 2 times with toluene. The mixture is stirred thoroughly and heated to 60°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to be <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours. 117.1g of vinyltrimethoxysilane, 90.17g of allyl glycidyl ether, and 392.4g of... 3-(methacryloyloxy)propyltrimethoxysilane was mixed evenly, diluted with toluene by 1:1, heated to 50°C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 100°C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-2 with a hydrogen content of 1.62 mmol / g. The C-3 is prepared by the following steps: 50g of hydrogen-containing silicone oil with a hydrogen content of 0.9wt% and a molecular weight of 2000 is diluted with toluene by 1:1 and set aside; 83.9g of tetramethyldivinyldisiloxane is added to a reaction flask, followed by 0.03g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%), mixed thoroughly, diluted with toluene by 1:1, stirred thoroughly, and heated to 50°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours; 60.4g of 1,1,3,3-tetramethyldisiloxane is added to a reaction flask and diluted with toluene by 1:1, stirred thoroughly, and heated to 50°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours; 5.7g of allyl glycidyl ether, 6.4g of n-butyl acrylate, and 12.4g of... 3-(methacryloyloxy)propyltrimethoxysilane and 67.1 g of tetramethyldivinyldisiloxane were mixed evenly, diluted with toluene by 1:1, heated to 50 °C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 100 °C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-3 with a vinyl content of 1.05 mmol / g. The C-4 is prepared by the following steps: 500g of end-side vinyl silicone oil, with a vinyl content of 0.7wt% and a molecular weight of 20,000, is diluted twice with toluene, and then 0.14g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) is added and mixed thoroughly. 17.5g of 1,1,3,3-tetramethyldisiloxane is added to a reaction flask and diluted twice with toluene, stirred thoroughly, and heated to 40°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours. 24.2g of tetramethyldivinyldisiloxane is added to a reaction flask and diluted twice with toluene, stirred thoroughly, and heated to 50°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours. 17.5g... 1,1,3,3-Tetramethyldisiloxane was added to a reaction flask and diluted with toluene by 1:

1. The mixture was stirred until homogeneous and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, with the reaction temperature controlled below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 3.23 g of 1,2-epoxy-4-vinylcyclohexane, 7.7 g of vinyltrimethoxysilane, and 10.5 g of tetramethyldisiloxane were mixed until homogeneous and diluted with toluene by 1:

1. The mixture was heated to 50°C and slowly added dropwise. After the addition was complete, the temperature was raised to 100°C and the reaction was maintained at this temperature for 4 hours. The reaction was then terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-4 with a vinyl content of 0.09 mmol / g. The C-6 is prepared by the following steps: 344.66 g of tetramethyltetravinylcyclotetrasiloxane is diluted 1 part with toluene, then 0.07 g of platinum-divinyltetramethyldisiloxane complex (Pt 20 wt%) is added and mixed thoroughly. 134.32 g of 1,1,3,3-tetramethyldisiloxane is added to a reaction flask and diluted 1 part with toluene, stirred thoroughly, and heated to 40°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours. 186.4 g of tetramethyldivinyldisiloxane is added to a reaction flask and diluted 1 part with toluene, stirred thoroughly, and heated to 50°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours. 134.32 g of... 1,1,3,3-Tetramethyldisiloxane was added to a reaction flask and diluted with toluene by half. The mixture was stirred thoroughly and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 186.4 g of tetramethyldivinyldisiloxane was added to a reaction flask and diluted with toluene by half. The mixture was stirred thoroughly and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 134.32 g of 1,1,3,3-Tetramethyldisiloxane was added to a reaction flask and diluted with toluene by half. The mixture was stirred thoroughly and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, maintaining the reaction temperature below 70°C. After the addition was complete, the reaction was maintained at this temperature for 2 hours. 248.35 g of... 3-(methacryloyloxy)propyltrimethoxysilane was diluted 1:1 with toluene, heated to 50°C, and the mixture obtained in the previous step was slowly added dropwise. After the addition was complete, the temperature was raised to 100°C, and the reaction was maintained for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-6 with a hydrogen content of 2.19 mmol / g.

4. A high-resilience one-component organopolysiloxane composition, characterized in that, It consists of the following components in parts by weight: Organopolysiloxane A-2, having at least two alkenyl groups per molecule: 5 parts; Organopolysiloxane B-1 with at least 2 Si-H bonds per molecule: 3.5 parts; Organopolysiloxane B-2 with at least 2 Si-H bonds per molecule: 2 parts; Hyperbranched organosilicon crosslinking agent C-3: 20 parts; Hyperbranched organosilicon crosslinking agent C-4: 40 parts; Hydrosilylation catalyst D-2: 0.2 parts; Fumed silica E-2: 40 parts; The A-2 is (CH2=CH(CH3)2SiO) 1 / 2 ) 0.2 (CH3)3SiO 1 / 2 ) 0.8 (SiO) 4 / 2 ) 1.25 ; The B-1 is (CH3)3SiO 1 / 2 (CH3)HSiO 2 / 2 ) 30 (CH3)2SiO 2 / 2 ) 50 ; The B-2 is ((CH3)2HSiO 1 / 2 (SiO) 4 / 2 ) 0.8 ; The D-2 is a capsule-type platinum catalyst with a Pt content of 5000 ppm; E-2 is fumed silica treated with methyl silicone oil. The C-3 is prepared by the following steps: 50g of hydrogen-containing silicone oil with a hydrogen content of 0.9wt% and a molecular weight of 2000 is diluted with toluene by 1:1 and set aside; 83.9g of tetramethyldivinyldisiloxane is added to a reaction flask, followed by 0.03g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%), mixed thoroughly, diluted with toluene by 1:1, stirred thoroughly, and heated to 50°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours; 60.4g of 1,1,3,3-tetramethyldisiloxane is added to a reaction flask and diluted with toluene by 1:1, stirred thoroughly, and heated to 50°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours; 5.7g of allyl glycidyl ether, 6.4g of n-butyl acrylate, and 12.4g of... 3-(methacryloyloxy)propyltrimethoxysilane and 67.1 g of tetramethyldivinyldisiloxane were mixed evenly, diluted with toluene by 1:1, heated to 50 °C, and the mixture obtained in the first step was slowly added dropwise. After the addition was complete, the temperature was raised to 100 °C, and the reaction was maintained at this temperature for 4 hours before the reaction was terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-3 with a vinyl content of 1.05 mmol / g. The C-4 is prepared by the following steps: 500g of end-side vinyl silicone oil, with a vinyl content of 0.7wt% and a molecular weight of 20,000, is diluted twice with toluene, and then 0.14g of platinum-divinyltetramethyldisiloxane complex (Pt 20wt%) is added and mixed thoroughly. 17.5g of 1,1,3,3-tetramethyldisiloxane is added to a reaction flask and diluted twice with toluene, stirred thoroughly, and heated to 40°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours. 24.2g of tetramethyldivinyldisiloxane is added to a reaction flask and diluted twice with toluene, stirred thoroughly, and heated to 50°C. The mixture obtained in the previous step is then slowly added dropwise, controlling the reaction temperature to <70°C. After the addition is complete, the reaction is maintained at this temperature for 2 hours. 17.5g... 1,1,3,3-Tetramethyldisiloxane was added to a reaction flask and diluted with toluene by 1:

1. The mixture was stirred until homogeneous and heated to 50°C. The mixture obtained in the previous step was then slowly added dropwise, with the reaction temperature controlled below 70°C. After the addition was complete, the mixture was kept at this temperature for 2 hours. 3.23 g of 1,2-epoxy-4-vinylcyclohexane, 7.7 g of vinyltrimethoxysilane, and 10.5 g of tetramethyldisiloxane were mixed until homogeneous and diluted with toluene by 1:

1. The mixture was heated to 50°C and slowly added dropwise. After the addition was complete, the temperature was raised to 100°C and the mixture was kept at this temperature for 4 hours. The reaction was then terminated. The solvent was removed by vacuum distillation to obtain hyperbranched organosilicon crosslinking agent C-4 with a vinyl content of 0.09 mmol / g.

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