Compound and preparation method thereof, flame retardant, heat-resistant additive, material modifier, silicone rubber material and preparation method thereof, and silicone rubber product

Abstract

The invention discloses a compound and a preparation method thereof, a flame retardant, a heat-resistant auxiliary agent, a material modifier, a silicone rubber material and a preparation method thereof, and a silicone rubber product, and the chemical structural general formula of the compound is as shown in the formula I. The compound provided by the invention contains a spirocyclic phosphate structure, a benzotriazole structure and the like, so that the compound is endowed with multiple functional characteristics such as excellent flame retardance, thermal stability and the like. Therefore, when the compound is applied to modification of materials such as silicone rubber, the flame retardant property, heat resistance and the like of the materials can be remarkably improved, and the application is wide.

Description

Technical Field

[0001] This application belongs to the field of silicone rubber materials, specifically relating to a compound and its preparation method, flame retardants, heat-resistant additives, material modifiers, silicone rubber materials and their preparation methods, and silicone rubber products. Background Technology

[0002] In the field of materials science, with the increasing demands for material performance across various industries, the development of novel materials with multifunctional properties has become a research hotspot. Especially in areas such as flame retardancy and heat resistance, traditional materials often struggle to meet the increasingly stringent application requirements.

[0003] Taking silicone rubber as an example, silicone rubber, as a high-performance elastomer material, has been widely used in many key fields such as aerospace, automotive industry, electronics, and medical equipment due to its excellent weather resistance and electrical insulation. However, the mechanical properties of silicone rubber deteriorate at high temperatures and its flame retardancy is poor, making it difficult for traditional silicone rubber to fully meet the needs of certain high-end application scenarios. Summary of the Invention

[0004] This application aims to at least partially solve one of the technical problems in related technologies. Therefore, the purpose of this application is to provide a compound and its preparation method, a flame retardant, a heat-resistant additive, a material modifier, a silicone rubber material and its preparation method, and silicone rubber products. The compound provided in this application contains spirocyclic phosphate structures and benzotriazole structures, endowing it with excellent flame retardancy and thermal stability, among other multifunctional properties. Therefore, when this compound is applied to the modification of materials such as silicone rubber, it can significantly improve the flame retardant and heat-resistant properties of the materials, and has a wide range of applications.

[0005] This application firstly discloses a compound. According to embodiments of this application, the general chemical structural formula of the compound is shown in Formula I;

[0006] Equation I: Where R is a substituent containing a benzotriazole structure.

[0007] The compounds described in the above embodiments of this application contain spirocyclic phosphate structures and benzotriazole structures, endowing them with excellent flame retardancy and thermal stability, among other multifunctional properties. Therefore, when applied to the modification of materials such as silicone rubber, these compounds can significantly improve the flame retardancy and heat resistance of the materials, making them widely applicable.

[0008] In addition, the compounds according to the above embodiments of this application may also have the following additional technical features:

[0009] In some embodiments of this application, the chemical structural formula of the compound is shown below:

[0010]

[0011] A second aspect of this application provides a method for preparing the compound described in any one of the first aspects. According to embodiments of this application, the method for preparing the compound includes the following steps:

[0012] The phosphorylating agent and pentaerythritol were reacted in the first reaction to give the intermediate product;

[0013] A second reaction is carried out between an amino-containing benzotriazole compound and the intermediate product to obtain the compound;

[0014] The chemical structural formula of the intermediate product is shown below:

[0015] X is a halogen atom.

[0016] The preparation method of the compounds described in the above embodiments of this application efficiently constructs chemical structural units such as spirocyclic phosphate structures and benzotriazole structures in the compounds through a two-step reaction, endowing them with multiple functional properties such as excellent flame retardancy and thermal stability.

[0017] In addition, the preparation method of the compound according to the above embodiments of this application may also have the following additional technical features:

[0018] In some embodiments of this application, the temperature of the first reaction is 65–75°C;

[0019] And / or, the duration of the first reaction is 3 to 5 hours;

[0020] And / or, the solvent for the first reaction includes at least one of acetonitrile, toluene, and N,N-dimethylformamide;

[0021] And / or, the molar ratio of the phosphorylating agent to the pentaerythritol is (1.5-2.5):(0.8-1.2), and the phosphorylating agent includes at least one of phosphorus oxychloride and phosphorus oxybromide.

[0022] In some embodiments of this application, the step of subjecting an amino-containing benzotriazole compound and the intermediate product to a second reaction to obtain the compound includes the following process;

[0023] Under the protection of an inert atmosphere and the action of an alkaline catalyst, the amino-containing benzotriazole compound and the intermediate product are subjected to the second reaction at a temperature of 65-75°C for 5-8 hours to obtain the compound;

[0024] The molar ratio of the amino-containing benzotriazole compound, the intermediate product, and the alkaline catalyst is (1.5–2.5):(0.8–1.2):(1.5–2.5), the amino-containing benzotriazole compound includes 2-aminobenzotriazole or 1-aminobenzotriazole, and the alkaline catalyst includes at least one of triethylamine, potassium carbonate, and sodium carbonate.

[0025] A third aspect of this application provides a flame retardant. According to embodiments of this application, the flame retardant comprises a compound as described in any one of the first aspects or a compound prepared using the method described in any one of the second aspects.

[0026] The flame retardant described in the above embodiments of this application comprises the compound described in any one of the first aspects or a compound prepared by the method described in any one of the second aspects. Therefore, the flame retardant possesses multiple functional properties such as excellent flame retardancy and thermal stability.

[0027] A fourth aspect of this application discloses a heat-resistant additive. According to embodiments of this application, the heat-resistant additive comprises the compound described in any one of the first aspects or a compound prepared using the method described in any one of the second aspects.

[0028] The heat-resistant additives described in the above embodiments of this application comprise the compounds described in any one of the first aspects or compounds prepared using the preparation method of the compounds described in any one of the second aspects. Therefore, the heat-resistant additives possess multiple functional properties such as excellent flame retardancy and thermal stability.

[0029] A fifth aspect of this application discloses a material modifier. According to embodiments of this application, the material modifier comprises a compound as described in any one of the first aspects or a compound prepared using the method described in any one of the second aspects.

[0030] The material modifier described in the above embodiments of this application comprises a compound as described in any one of the first aspects or a compound prepared using the method described in any one of the second aspects. Therefore, the material modifier possesses multiple functional properties such as excellent flame retardancy and thermal stability.

[0031] A sixth aspect of this application discloses a silicone rubber material. According to embodiments of this application, the raw materials for this silicone rubber material include the compounds described in any one of the first aspects or compounds prepared using the preparation method of the compounds described in any one of the second aspects.

[0032] The silicone rubber material described in the above embodiments of this application is modified by introducing the compound described in any one of the first aspects or by using the preparation method of the compound described in any one of the second aspects. As a result, the overall properties of the silicone rubber material, such as flame retardancy and heat resistance, are significantly improved.

[0033] In addition, the silicone rubber material according to the above embodiments of this application may also have the following additional technical features:

[0034] In some embodiments of this application, the silicone rubber material comprises the following raw materials in parts by weight:

[0035] The mixture comprises 73-87 parts of silicone rubber matrix, 6-16 parts of the compound, 3-5 parts of crosslinking agent, and 0.01-0.03 parts of catalyst.

[0036] In some embodiments of this application, the silicone rubber matrix includes at least one of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber;

[0037] And / or, the crosslinking agent includes at least one of methyl hydrogen silicone oil, methyl phenyl hydrogen silicone oil and tetramethyldihydrodisiloxane;

[0038] And / or, the catalyst comprises a platinum catalyst, wherein the platinum catalyst comprises at least one of chloroplatinic acid hexahydrate and a cassette catalyst.

[0039] In some embodiments of this application, the raw materials of the silicone rubber material further include, by weight:

[0040] 7-13 parts of reinforcing agent.

[0041] In some embodiments of this application, the reinforcing agent includes at least one of silica, iron oxide, and titanium oxide.

[0042] In some embodiments of this application, the tensile strength of the silicone rubber material is 11.3–12.2 MPa;

[0043] And / or, the limiting oxygen index of the silicone rubber material is 31.0 to 33.1%;

[0044] And / or, the tensile strength retention rate of the silicone rubber material before and after thermal cycling treatment at 350°C is 97.1% to 97.6%.

[0045] A seventh aspect of this application provides a method for preparing the silicone rubber material described in any one of the sixth aspects above. According to an embodiment of this application, the method for preparing the silicone rubber material includes the following steps:

[0046] The raw materials of silicone rubber are mixed to obtain a compound;

[0047] The compound is vulcanized to obtain the silicone rubber material.

[0048] The present application describes a method for preparing silicone rubber materials according to the embodiments described above. This method involves introducing the aforementioned compounds through compounding and combining this with a vulcanization process to modify the silicone rubber material. As a result, the overall performance of the silicone rubber material, including its flame retardant and heat resistance properties, is significantly improved, successfully producing a silicone rubber material that combines high-temperature resistance and excellent flame retardant properties.

[0049] In addition, the method for preparing the silicone rubber material according to the above embodiments of this application may also have the following additional technical features:

[0050] In some embodiments of this application, the step of mixing raw materials of silicone rubber to obtain a compound includes the following processes:

[0051] The raw materials, excluding the crosslinking agent and catalyst, are intensively mixed at 50-80°C for 10-15 minutes to obtain a mixture.

[0052] The mixture, the crosslinking agent, and the catalyst are subjected to open milling at a temperature of 40–80°C for 10–30 min to obtain the compound.

[0053] In some embodiments of this application, the vulcanization temperature is 120–180°C;

[0054] And / or, the vulcanization pressure is 5-10 MPa;

[0055] And / or, the vulcanization time is 5 to 15 minutes.

[0056] The eighth aspect of this application discloses a silicone rubber article. According to an embodiment of this application, the raw materials for the silicone rubber article include the compound described in any one of the first aspects, the compound prepared by the method described in any one of the second aspects, the silicone rubber material described in any one of the sixth aspects, or the silicone rubber material prepared by the method described in any one of the seventh aspects.

[0057] The silicone rubber product described in the above embodiments of this application is made from raw materials including the aforementioned compounds or silicone rubber materials. Therefore, the silicone rubber product possesses excellent flame retardant properties and heat resistance, among other properties.

[0058] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Detailed Implementation

[0059] The embodiments of this application are described in detail below by way of example, and are intended to explain this application, but should not be construed as limiting this application.

[0060] This application firstly discloses a compound. According to embodiments of this application, the general chemical structural formula of the compound is shown in Formula I;

[0061] Equation I: Where R is a substituent containing a benzotriazole structure.

[0062] The compounds described in the above embodiments of this application contain a spirocyclic phosphate structure (i.e., the chemical structure in Formula I excluding R) and a benzotriazole structure (a fused ring structure formed by the fusion of a benzene ring and a 1,2,3-triazole ring), endowing them with excellent flame retardancy and thermal stability, among other multifunctional properties. Therefore, when applied to the modification of materials such as silicone rubber, these compounds can significantly improve the flame retardant and heat resistance properties of the materials, making them widely applicable. Specifically:

[0063] 1) The benzotriazole structure in this compound exhibits high conjugation effect and aromatic stability, making it less prone to bond breaking or decomposition at high temperatures. Furthermore, the nitrogen atom on the azole ring can participate in π-conjugation through lone pair electrons, further enhancing the compound's thermal stability. Simultaneously, the spirocyclic phosphate structure in the compound can capture highly reactive free radicals such as H· and HO· through gas-phase free radical capture, interrupting the combustion chain reaction. It can also condense into a dense, heat-insulating, and oxygen-barrier char layer, effectively preventing heat transfer, inhibiting the volatilization of combustible gases, and blocking oxygen from entering the combustion zone, thus achieving a self-extinguishing effect. Moreover, the char products of the spirocyclic phosphate structure have a high char residue rate, which can improve the mechanical strength of the char layer, prevent it from cracking during combustion, maintain the integrity of the flame-retardant barrier, and further improve flame-retardant performance. Therefore, the compound provided in this application, through chemical structural units such as the spirocyclic phosphate structure and the benzotriazole structure, endows it with excellent flame-retardant and thermal stability, among other multifunctional properties.

[0064] 2) Compared to inorganic heat-resistant fillers, the compounds provided in this application are organic molecules, which exhibit better compatibility with materials such as silicone rubber and have a tighter interfacial bond. Therefore, the compounds provided in this application can more effectively improve the heat resistance and flame retardant properties of materials such as silicone rubber.

[0065] According to some specific embodiments of this application, R is selected from any of the following substituents:

[0066]

[0067] It should be noted that in the chemical structures of the above substituents It only indicates that a chemical bond is formed or broken at that point, and is not part of a substituent.

[0068] According to some specific embodiments of this application, the chemical structural formula of the compound is shown below:

[0069]

[0070] Based on the above, the compounds provided in this application not only contain chemical structural units such as spirocyclic phosphate structure and benzotriazole structure, but also have phosphorus atoms and nitrogen atoms directly connected in the compound, forming a PN synergistic flame retardant component, which further improves its flame retardant performance.

[0071] A second aspect of this application provides a method for preparing the compound described in any one of the first aspects. According to embodiments of this application, the method for preparing the compound includes the following steps:

[0072] The phosphorylating agent and pentaerythritol were reacted in the first reaction to give the intermediate product;

[0073] A second reaction is carried out between an amino-containing benzotriazole compound and the intermediate product to obtain the compound;

[0074] The chemical structural formula of the intermediate product is shown below:

[0075] X is a halogen atom.

[0076] The preparation method of the compounds described in the above embodiments of this application efficiently and successfully constructs chemical structural units such as spirocyclic phosphate structures and benzotriazole structures in the compounds through a two-step reaction, endowing them with multiple functional properties such as excellent flame retardancy and thermal stability. Specifically:

[0077] Step 1: This application uses phosphorylation reagents such as phosphorus oxychloride and pentaerythritol as raw materials to carry out a phosphorylation reaction (an organic chemical reaction in which a phosphorylation reagent such as phosphorus oxychloride reacts with a hydroxyl-containing compound such as an alcohol to generate a phosphate ester compound, i.e., the first reaction), to obtain an intermediate product. Taking phosphorus oxychloride and pentaerythritol as an example, the specific reaction process is as follows:

[0078]

[0079] Step 2: This application uses amino-containing benzotriazole compounds, such as 2-aminobenzotriazole, and the intermediate obtained in Step 1 as starting materials to carry out a nucleophilic substitution reaction (specifically, the amino group in the amino-containing benzotriazole compound undergoes nucleophilic substitution with the halogen group in the intermediate; i.e., the second reaction) to obtain the target product. Taking the reaction of 2-aminobenzotriazole and the intermediate as an example, the specific reaction process is as follows:

[0080]

[0081] According to some specific embodiments of this application, the temperature of the first reaction is 65-75°C;

[0082] And / or, the duration of the first reaction is 3 to 5 hours;

[0083] And / or, the solvent for the first reaction includes at least one of acetonitrile, toluene, and N,N-dimethylformamide;

[0084] And / or, the molar ratio of the phosphorylating agent to the pentaerythritol is (1.5-2.5):(0.8-1.2), for example, it can be 1.5:1, 1.5:0.8, 1.5:1.2, 2:1, 2:1.2, 2.5:1, etc., preferably 2:1, and the phosphorylating agent includes at least one of phosphorus oxychloride and phosphorus oxybromide, preferably phosphorus oxychloride.

[0085] In the embodiments of this application, the reaction temperature of the first reaction can be 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, etc., preferably 68°C; the reaction time can be 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, etc., preferably 4 hours.

[0086] In the embodiments of this application, the reaction solvent for the first reaction is not particularly limited. A commonly used solvent in the art can be selected based on the solubility of the reactants and the reaction temperature. For example, an organic solvent such as acetonitrile can be used as the reaction solvent for the first reaction. Furthermore, the post-purification processing of the product after the first reaction is also not particularly limited. It generally includes preliminary separation steps such as extraction, filtration, and centrifugation; concentration and drying steps such as rotary evaporation, freeze-drying, and vacuum drying; and product purification steps such as recrystallization, column chromatography, distillation, activated carbon decolorization, and washing. Specifically, the post-purification processing of the product after the first reaction can be performed as follows: After the reaction, cool to room temperature, rotary evaporate, wash repeatedly with dichloromethane and anhydrous ethanol, and after washing, vacuum dry to obtain the intermediate product.

[0087] According to some specific embodiments of this application, the step of subjecting an amino-containing benzotriazole compound and the intermediate product to a second reaction to obtain the compound includes the following process;

[0088] Under the protection of an inert atmosphere and the action of an alkaline catalyst, the amino-containing benzotriazole compound and the intermediate product are subjected to the second reaction at a temperature of 65-75°C for 5-8 hours to obtain the compound;

[0089] The molar ratio of the amino-containing benzotriazole compound, the intermediate product, and the alkaline catalyst is (1.5–2.5):(0.8–1.2):(1.5–2.5), for example, 2:1:1.5, 2:1:2, 2:1:1.8, 2.2:1:1.5, 2.2:1:2, etc.; the amino-containing benzotriazole compound includes 2-aminobenzotriazole or 1-aminobenzotriazole; the alkaline catalyst includes at least one of triethylamine, potassium carbonate, and sodium carbonate.

[0090] In the embodiments of this application, the reaction temperature of the second reaction can be 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, etc., preferably 70°C; the reaction time can be 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, etc., preferably 6 hours.

[0091] In the embodiments of this application, the reaction solvent for the second reaction is not particularly limited. A commonly used solvent in the art can be selected based on the solubility of the reactants and the reaction temperature. For example, an organic solvent such as toluene can be used as the reaction solvent for the second reaction. Furthermore, the post-purification processing of the product after the second reaction is also not particularly limited. It generally includes preliminary separation steps such as extraction, filtration, and centrifugation; concentration and drying steps such as rotary evaporation, freeze-drying, and vacuum drying; and product purification steps such as recrystallization, column chromatography, distillation, activated carbon decolorization, and washing. Specifically, the post-purification processing of the product after the second reaction can be performed as follows: After the reaction, cool to room temperature, remove part of the solvent by rotary evaporation, then perform column chromatography purification using a benzene-based solvent (such as benzene, toluene, etc.)-ethyl acetate (2:1, v / v) elution system, remove the eluent by rotary evaporation, and vacuum dry to obtain the target product.

[0092] A third aspect of this application provides a flame retardant. According to embodiments of this application, the flame retardant comprises a compound as described in any one of the first aspects or a compound prepared using the method described in any one of the second aspects.

[0093] The flame retardant described in the above embodiments of this application comprises the compound described in any one of the first aspects or a compound prepared by the method described in any one of the second aspects. Therefore, the flame retardant possesses multiple functional properties such as excellent flame retardancy and thermal stability.

[0094] A fourth aspect of this application discloses a heat-resistant additive. According to embodiments of this application, the heat-resistant additive comprises the compound described in any one of the first aspects or a compound prepared using the method described in any one of the second aspects.

[0095] The heat-resistant additives described in the above embodiments of this application comprise the compounds described in any one of the first aspects or compounds prepared using the preparation method of the compounds described in any one of the second aspects. Therefore, the heat-resistant additives possess multiple functional properties such as excellent flame retardancy and thermal stability.

[0096] A fifth aspect of this application discloses a material modifier. According to embodiments of this application, the material modifier comprises a compound as described in any one of the first aspects or a compound prepared using the method described in any one of the second aspects.

[0097] The material modifier described in the above embodiments of this application comprises a compound as described in any one of the first aspects or a compound prepared using the method described in any one of the second aspects. Therefore, the material modifier possesses multiple functional properties such as excellent flame retardancy and thermal stability.

[0098] A sixth aspect of this application discloses a silicone rubber material. According to embodiments of this application, the raw materials for this silicone rubber material include the compounds described in any one of the first aspects or compounds prepared using the preparation method of the compounds described in any one of the second aspects.

[0099] The silicone rubber material described in the above embodiments of this application is modified by introducing the compound described in any one of the first aspects or by using the preparation method of the compound described in any one of the second aspects. As a result, the overall properties of the silicone rubber material, such as flame retardancy and heat resistance, are significantly improved.

[0100] In some other embodiments of this application, the silicone rubber material comprises the following raw materials in parts by weight:

[0101] The mixture comprises 73-87 parts of silicone rubber matrix, 6-16 parts of the compound, 3-5 parts of crosslinking agent, and 0.01-0.03 parts of catalyst.

[0102] In the embodiments of this application, the aforementioned silicone rubber matrix is ​​a type of polymer with silicon-oxygen (Si-O) bonds as the main chain, and its side chains are connected to organic groups (such as methyl, phenyl, vinyl, etc.) through silicon atoms. The typical structural formula is: [-Si(R)2-O-]n; where R represents an organic group (such as -CH3, -C6H5), n is the degree of polymerization, and its weight parts can be 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, etc.

[0103] In the embodiments of this application, the weight parts of the above-mentioned compound may be 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, etc.

[0104] In the embodiments of this application, the weight parts of the crosslinking agent can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.

[0105] In the embodiments of this application, the weight parts of the catalyst may be 0.01 parts, 0.02 parts, 0.03 parts, etc.

[0106] In some other embodiments of this application, the silicone rubber matrix includes at least one of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber, preferably methyl vinyl silicone rubber;

[0107] And / or, the crosslinking agent includes at least one of methyl hydrogen silicone oil, methyl phenyl hydrogen silicone oil and tetramethyldihydrodisiloxane, preferably hydrogen silicone oils such as methyl hydrogen silicone oil and methyl phenyl hydrogen silicone oil;

[0108] And / or, the catalyst comprises a platinum catalyst, the platinum catalyst comprising at least one of chloroplatinic acid hexahydrate and a cassette catalyst, preferably chloroplatinic acid hexahydrate.

[0109] In some other embodiments of this application, the raw materials of the silicone rubber material further include, by weight:

[0110] 7-13 parts of reinforcing agent.

[0111] In the embodiments of this application, the weight parts of the above-mentioned reinforcing agent may be 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, etc.

[0112] In some other embodiments of this application, the reinforcing agent includes at least one of silica, iron oxide, and titanium oxide.

[0113] In some other embodiments of this application, the tensile strength of the silicone rubber material is 11.3 to 12.2 MPa;

[0114] And / or, the limiting oxygen index of the silicone rubber material is 31.0 to 33.1%;

[0115] And / or, the tensile strength retention rate of the silicone rubber material before and after thermal cycling treatment at 350°C is 97.1% to 97.6%.

[0116] In the embodiments of this application, the tensile strength of the above-mentioned silicone rubber material is maintained at 11.3 to 12.2 MPa, the limiting oxygen index is maintained at 31.0 to 33.1%, and the tensile strength retention rate before and after the 350°C heat cycling treatment is maintained at 97.1% to 97.6%, indicating that it has excellent mechanical properties, flame retardant properties and heat resistance properties.

[0117] A seventh aspect of this application provides a method for preparing the silicone rubber material described in any one of the sixth aspects above. According to an embodiment of this application, the method for preparing the silicone rubber material includes the following steps:

[0118] The raw materials of silicone rubber are mixed to obtain a compound;

[0119] The compound is vulcanized to obtain the silicone rubber material.

[0120] The present application describes a method for preparing silicone rubber materials according to the embodiments described above. This method involves introducing the aforementioned compounds through compounding and combining this with a vulcanization process to modify the silicone rubber material. As a result, the overall performance of the silicone rubber material, including its flame retardant and heat resistance properties, is significantly improved, successfully producing a silicone rubber material that combines high-temperature resistance and excellent flame retardant properties.

[0121] In some other embodiments of this application, the step of mixing the raw materials of silicone rubber to obtain a compound includes the following processes:

[0122] The raw materials, excluding the crosslinking agent and catalyst, are intensively mixed at 50-80°C for 10-15 minutes to obtain a mixture.

[0123] The mixture, the crosslinking agent, and the catalyst are subjected to open milling at a temperature of 40–80°C for 10–30 min to obtain the compound.

[0124] In the embodiments of this application, the mixing temperature can be 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃, 59℃, 60℃, 61℃, 62℃, 63℃, 64℃, 65℃, 66℃, 67℃, 68℃, 69℃, 70℃, 71℃, 72℃, 73℃, 74℃, 75℃, 76℃, 77℃, 78℃, 79℃, 80℃, etc., and the time can be 10min, 11min, 12min, 13min, 14min, 15min, etc.

[0125] In the embodiments of this application, the temperature of the above-mentioned smelting can be 40°C, 50°C, 60°C, 70°C, 80°C, etc., and the time can be 10 min, 15 min, 20 min, 25 min, 25 min, etc.

[0126] In some other embodiments of this application, the vulcanization temperature is 120–180°C;

[0127] And / or, the vulcanization pressure is 5-10 MPa;

[0128] And / or, the vulcanization time is 5-15 min.

[0129] In the embodiments of this application, the vulcanization temperature can be 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, etc.; the vulcanization pressure can be 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, etc.; and the vulcanization time can be 5 min, 7 min, 9 min, 12 min, 15 min, etc.

[0130] The eighth aspect of this application discloses a silicone rubber article. According to an embodiment of this application, the raw materials for the silicone rubber article include the compound described in any one of the first aspects, the compound prepared by the method described in any one of the second aspects, the silicone rubber material described in any one of the sixth aspects, or the silicone rubber material prepared by the method described in any one of the seventh aspects.

[0131] The silicone rubber product described in the above embodiments of this application. The raw materials for this silicone rubber product include the aforementioned compounds or the aforementioned silicone rubber materials. Therefore, this silicone rubber product possesses excellent flame retardant and heat resistance properties, etc. Specifically, the silicone rubber product described in this application is a high-temperature resistant, flame-retardant silicone rubber product, which may include, for example, insulating sheaths, sealing gaskets, plugs, sockets, etc., for wires and cables.

[0132] The embodiments of this application are described in detail below. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. In addition, unless otherwise specified, all reagents used in the following embodiments are commercially available or can be synthesized according to the methods described herein or known methods. For reaction conditions not listed, they are also readily available to those skilled in the art.

[0133] Example 1

[0134] This embodiment provides a compound, the chemical structural formula of which is shown in Formula II below;

[0135] Formula II:

[0136] This embodiment also provides a method for preparing the above-mentioned compound, including the following steps:

[0137] S1: Add 35.7g of phosphorus oxychloride, 13.6g of pentaerythritol and 100mL of anhydrous acetonitrile to a three-necked flask, stir well, heat to 68℃, and stir at a constant temperature for 4h. After the reaction is complete, cool, rotary evaporate, wash and dry to obtain the intermediate product.

[0138] S2: 29.3 g of 2-aminobenzotriazole, 29.5 g of the intermediate obtained in S1, 120 mL of toluene and 20.2 g of triethylamine were added to a flask, stirred until homogeneous, and nitrogen gas was introduced. The mixture was heated to 70 °C and stirred at a constant temperature for 6 h. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed by rotary evaporation, and then purified by column chromatography using a benzene-ethyl acetate (2:1, v / v) elution system. The eluent was removed by rotary evaporation and the mixture was dried under vacuum to obtain the target product - the compound shown in Formula II.

[0139] The product yield of the compound shown in Formula II obtained in this embodiment was 83.5%.

[0140] Example 2

[0141] This embodiment provides a compound represented by Formula II and its preparation method, which differs from Example 1 only in that:

[0142] (1) Step S1: Weigh 71.4g of phosphorus oxychloride and 27.2g of pentaerythritol as raw materials and 200mL of anhydrous acetonitrile as solvent.

[0143] (2) Step S2: Weigh 58.6g of 2-aminobenzotriazole and 59.0g of intermediate product as raw materials, 240mL of toluene as solvent and 40.4g of triethylamine as catalyst.

[0144] The product yield of the compound shown in Formula II obtained in this embodiment was 84.2%.

[0145] Example 3

[0146] This embodiment provides a compound represented by Formula II and its preparation method, which differs from Example 1 only in that:

[0147] (1) Step S1: Adjust the molar ratio of phosphorus oxychloride and pentaerythritol to 1.5:0.8, adjust the temperature of the constant temperature stirring reaction to 65℃, and adjust the time of the constant temperature stirring reaction to 3 hours.

[0148] (2) Step S2: Adjust the molar ratio of 2-aminobenzotriazole, intermediate product and triethylamine to 1.5:0.8:1.5, adjust the temperature of the constant temperature stirring reaction to 65℃, and adjust the time of the constant temperature stirring reaction to 5 hours.

[0149] The product yield of the compound shown in Formula II obtained in this embodiment was 82.7%.

[0150] Example 4

[0151] This embodiment provides a compound represented by Formula II and its preparation method, which differs from Example 1 only in that:

[0152] (1) Step S1: Adjust the molar ratio of phosphorus oxychloride and pentaerythritol to 2.5:1.2, adjust the temperature of the constant temperature stirring reaction to 75℃, and adjust the time of the constant temperature stirring reaction to 5 hours.

[0153] (2) Step S2: Adjust the molar ratio of 2-aminobenzotriazole, intermediate product and triethylamine to 2.5:1.2:2.5, adjust the temperature of the constant temperature stirring reaction to 75℃, and adjust the time of the constant temperature stirring reaction to 8 hours.

[0154] The product yield of the compound shown in Formula II obtained in this embodiment was 86.5%.

[0155] Example 5

[0156] This embodiment provides a compound and its preparation method, which differs from Example 1 only in that:

[0157] (1) Step S2: Change 2-aminobenzotriazole to 1-aminobenzotriazole.

[0158] The product yield of the compound obtained in this example was 81.1%.

[0159] Example 6

[0160] This embodiment provides a silicone rubber material, which, by weight parts, comprises the following raw materials:

[0161] 73 parts of silicone rubber matrix (specifically methyl vinyl silicone rubber, purchased from Chongqing Ruiya Biotechnology Co., Ltd., product CAS number 67762-94-1), 6 parts of the compound shown in Formula II, 3 parts of crosslinking agent (specifically hydrogen-containing silicone oil, purchased from Wuhan Jushun Chemical Co., Ltd., product CAS number 63148-57-2), 0.01 parts of catalyst (specifically chloroplatinic acid hexahydrate) and 7 parts of reinforcing agent (specifically silica).

[0162] This embodiment also provides a method for preparing the above-mentioned silicone rubber material, including the following steps:

[0163] Step (1): Mix the raw materials, except for the crosslinking agent and catalyst, at 50°C for 10 minutes to obtain a mixture;

[0164] Step (2): The mixture, crosslinking agent and catalyst obtained in step (1) are subjected to open milling at 40°C for 10 min to obtain the compound;

[0165] Step (3): The compound obtained in step (2) is vulcanized at 120°C and 5 MPa for 5 minutes to obtain silicone rubber material.

[0166] Example 7

[0167] This embodiment provides a silicone rubber material, which, by weight parts, comprises the following raw materials:

[0168] 80 parts of silicone rubber matrix (specifically methyl vinyl silicone rubber, purchased from Chongqing Ruiya Biotechnology Co., Ltd., product CAS number 67762-94-1), 11 parts of the compound shown in Formula II, 4 parts of crosslinking agent (specifically methyl hydrogen silicone oil, purchased from Wuhan Jushun Chemical Co., Ltd., product CAS number 63148-57-2), 0.02 parts of catalyst (specifically chloroplatinic acid hexahydrate) and 10 parts of reinforcing agent (specifically iron oxide).

[0169] This embodiment also provides a method for preparing the above-mentioned silicone rubber material, including the following steps:

[0170] Step (1): Mix the raw materials, except for the crosslinking agent and catalyst, at 65°C for 15 minutes to obtain a mixture;

[0171] Step (2): The mixture, crosslinking agent and catalyst obtained in step (1) are subjected to open milling at 60°C for 20 min to obtain the compound;

[0172] Step (3): The compound obtained in step (2) is vulcanized at 150°C and 8 MPa for 10 minutes to obtain silicone rubber material.

[0173] Example 8

[0174] This embodiment provides a silicone rubber material, which, by weight parts, comprises the following raw materials:

[0175] 87 parts of silicone rubber matrix (specifically methyl vinyl silicone rubber, purchased from Chongqing Ruiya Biotechnology Co., Ltd., product CAS number 67762-94-1), 16 parts of the compound shown in Formula II, 5 parts of crosslinking agent (specifically hydrogen-containing silicone oil, purchased from Wuhan Jushun Chemical Co., Ltd., product CAS number 63148-57-2), 0.03 parts of catalyst (specifically chloroplatinic acid hexahydrate) and 13 parts of reinforcing agent (specifically titanium dioxide).

[0176] This embodiment also provides a method for preparing the above-mentioned silicone rubber material, including the following steps:

[0177] Step (1): Mix the raw materials except for the crosslinking agent and catalyst at 80°C for 15 minutes to obtain a mixture;

[0178] Step (2): The mixture, crosslinking agent and catalyst obtained in step (1) are subjected to open milling at 80°C for 30 min to obtain the compound;

[0179] Step (3): The compound obtained in step (2) is vulcanized at 180°C and 10 MPa for 15 minutes to obtain silicone rubber material.

[0180] Example 9

[0181] This embodiment provides a silicone rubber material and its preparation method, which differs from Embodiment 8 only in that:

[0182] (1) The compound shown in Formula II was modified to the compound obtained in Example 5.

[0183] Example 10

[0184] This embodiment provides a silicone rubber material and its preparation method, which differs from Embodiment 8 only in that:

[0185] (1) The weight of the reinforcing agent is adjusted to 0 parts (i.e. no reinforcing agent is added).

[0186] Example 11

[0187] This embodiment provides a silicone rubber material and its preparation method, which differs from Embodiment 8 only in that:

[0188] (1) The raw material of the silicone rubber matrix was adjusted to methyl phenyl vinyl silicone rubber (purchased from Anhui Aiyota Silicone Oil Co., Ltd., product CAS number is 68083-18-1);

[0189] (2) The raw material of the crosslinking agent was adjusted to methyl phenyl hydrogen-containing silicone oil (purchased from Anhui Aiyota Silicone Oil Co., Ltd., product CAS number 17875-55-7);

[0190] (3) The raw material for the catalyst was adjusted to a cassiterite catalyst.

[0191] Comparative Example 1

[0192] This comparative example provides a silicone rubber material and its preparation method, which differs from Example 8 only in that:

[0193] (1) Adjust the compound shown in Formula II to a commercially available heat stabilizer (the commercially available heat stabilizer is benzotriazole or benzotriazole, purchased from Shaoguan Yang'an Chemical Co., Ltd., CAS No. 95-14-7).

[0194] Comparative Example 2

[0195] This comparative example provides a commercially available silicone rubber material (purchased from Shin-Etsu Chemical Co., Ltd., Japan, product model KE951U).

[0196] Test case

[0197] This test example performs performance tests on the silicone rubber materials obtained in Examples 6-11 and Comparative Examples 1-2.

[0198] The testing standards and methods are as follows:

[0199] (1) The tensile strength was determined in accordance with the national standard GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber";

[0200] (2) The limiting oxygen index of the sample was determined according to the national standard GB / T 10707 "Determination of the flammability of rubber";

[0201] (3) The sample was subjected to three thermal cycles. Specifically, the sample was heated to 350°C at a heating rate of 10°C / min, and then cooled to room temperature by air cooling. The tensile strength after the three thermal cycles was measured (refer to the test method in (1)) and the tensile strength retention rate was calculated. Tensile strength retention rate = tensile strength after test / tensile strength before test × 100%.

[0202] The test results are shown in Table 1.

[0203] Table 1

[0204]

[0205]

[0206] As shown in Table 1, the tensile strength of the silicone rubber prepared in the embodiments of the present invention is significantly improved after the addition of reinforcing agents. Furthermore, compared with the comparative examples, the embodiments, after adding the self-made compound, not only have a high tensile strength retention rate and good heat resistance after three thermal cycles, but also have an improved limiting oxygen index. In addition, the silicone rubber matrix of Example 11 contains benzene rings, resulting in even higher tensile strength. In summary, the present invention has important application value in the field of silicone rubber technology.

[0207] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, silicone rubber material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, silicone rubber materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0208] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A compound, characterized in that, The general chemical structural formula of the compound is shown in Formula I; Equation I: Where R is a substituent containing a benzotriazole structure.

2. The compound according to claim 1, characterized in that, The chemical structural formula of the compound is shown below:

3. A method for preparing a compound according to any one of claims 1 to 2, characterized in that, The method for preparing the compound includes the following steps: The phosphorylating agent and pentaerythritol were reacted in the first reaction to give the intermediate product; A second reaction is carried out between an amino-containing benzotriazole compound and the intermediate product to obtain the compound; The chemical structural formula of the intermediate product is shown below: X is a halogen atom.

4. The method for preparing the compound according to claim 3, characterized in that, The temperature of the first reaction is 65–75°C; And / or, the duration of the first reaction is 3 to 5 hours; And / or, the solvent for the first reaction includes at least one of acetonitrile, toluene, and N,N-dimethylformamide; And / or, the molar ratio of the phosphorylating agent to the pentaerythritol is (1.5-2.5):(0.8-1.2), and the phosphorylating agent includes at least one of phosphorus oxychloride and phosphorus oxybromide.

5. The method for preparing the compound according to claim 3, characterized in that, The step of reacting an amino-containing benzotriazole compound with the intermediate to obtain the compound includes the following process; Under the protection of an inert atmosphere and the action of an alkaline catalyst, the amino-containing benzotriazole compound and the intermediate product are subjected to the second reaction at a temperature of 65-75°C for 5-8 hours to obtain the compound; The molar ratio of the amino-containing benzotriazole compound, the intermediate product, and the alkaline catalyst is (1.5–2.5):(0.8–1.2):(1.5–2.5), the amino-containing benzotriazole compound includes 2-aminobenzotriazole or 1-aminobenzotriazole, and the alkaline catalyst includes at least one of triethylamine, potassium carbonate, and sodium carbonate.

6. A flame retardant, characterized in that, The flame retardant includes the compound according to any one of claims 1 to 2 or the compound prepared by the method of any one of claims 3 to 5.

7. A heat-resistant additive, characterized in that, The heat-resistant additive includes the compound according to any one of claims 1 to 2 or the compound prepared by the method of any one of claims 3 to 5.

8. A material modifier, characterized in that, The material modifier includes the compound according to any one of claims 1 to 2 or the compound prepared by the method of any one of claims 3 to 5.

9. A silicone rubber material, characterized in that, The raw materials for the silicone rubber material include the compounds according to any one of claims 1 to 2 or the compounds prepared by the method of any one of claims 3 to 5.

10. The silicone rubber material according to claim 9, characterized in that, The silicone rubber material comprises the following raw materials in parts by weight: The mixture comprises 73-87 parts of silicone rubber matrix, 6-16 parts of the compound, 3-5 parts of crosslinking agent, and 0.01-0.03 parts of catalyst.

11. The silicone rubber material according to claim 10, characterized in that, The silicone rubber matrix includes at least one of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber; And / or, the crosslinking agent includes at least one of methyl hydrogen silicone oil, methyl phenyl hydrogen silicone oil and tetramethyldihydrodisiloxane; And / or, the catalyst comprises a platinum catalyst, wherein the platinum catalyst comprises at least one of chloroplatinic acid hexahydrate and a cassette catalyst.

12. The silicone rubber material according to any one of claims 9 to 11, characterized in that, The raw materials of the silicone rubber material, by weight, further include: 7-13 parts of reinforcing agent.

13. The silicone rubber material according to claim 12, characterized in that, The reinforcing agent includes at least one of silica, iron oxide, and titanium oxide.

14. The silicone rubber material according to claim 13, characterized in that, The tensile strength of the silicone rubber material is 11.3–12.2 MPa; And / or, the limiting oxygen index of the silicone rubber material is 31.0 to 33.1%; And / or, the tensile strength retention rate of the silicone rubber material before and after thermal cycling treatment at 350°C is 97.1% to 97.6%.

15. A method for preparing a silicone rubber material according to any one of claims 9 to 14, characterized in that, The preparation method of the silicone rubber material includes the following steps: The raw materials of silicone rubber are mixed to obtain a compound; The compound is vulcanized to obtain the silicone rubber material.

16. The method for preparing silicone rubber material according to claim 15, characterized in that, The steps for mixing raw materials of silicone rubber to obtain a compound include the following processes: The raw materials, excluding the crosslinking agent and catalyst, are intensively mixed at 50-80°C for 10-15 minutes to obtain a mixture. The mixture, the crosslinking agent, and the catalyst are subjected to open milling at a temperature of 40–80°C for 10–30 min to obtain the compound.

17. The method for preparing silicone rubber material according to claim 15, characterized in that, The vulcanization temperature is 120–180°C; And / or, the vulcanization pressure is 5-10 MPa; And / or, the vulcanization time is 5 to 15 minutes.

18. A silicone rubber product, characterized in that, The raw materials for the silicone rubber products include the compounds according to any one of claims 1 to 2 or the compounds prepared by the method of the compounds according to any one of claims 3 to 5, the silicone rubber materials according to any one of claims 9 to 14 or the silicone rubber materials prepared by the method of the silicone rubber materials according to any one of claims 15 to 17.

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