A silicone rubber material, a preparation method thereof, a silicone rubber component and an electronic device

Abstract

This application discloses a silicone rubber material and its preparation method, silicone parts, and electronic devices, relating to the field of silicone rubber technology. The disclosed silicone rubber material, by weight parts, comprises: 40-100 parts of a vinyl-containing siloxane, 10-50 parts of reinforcing filler, 0.001-10 parts of a catalyst, 0.002-30 parts of a crosslinking agent, 0.001-10 parts of an inhibitor, and 1-50 parts of a high-density filler, wherein the high-density filler includes carboxylated nano-gadolinium oxide. This application increases the density of the silicone rubber material without affecting its mechanical properties.

Description

Technical Field

[0001] This application relates to the field of silicone rubber technology, and in particular to a silicone rubber material and its preparation method, silicone parts, and electronic devices. Background Technology

[0002] Silicone rubber is a high-performance elastomer material with polyorganosiloxane as the main chain. Due to its excellent high and low temperature resistance (usually it can be used stably in the range of -50~200℃), good electrical insulation, weather resistance, anti-aging properties and physiological inertness, it is widely used in the field of wearable devices to make various silicone parts, such as smart watch straps, wristbands, etc.

[0003] However, silicone rubber has a low bulk density, resulting in lightweight silicone parts that are not very durable, which can affect the stability of the device during wear. While the density can be increased by adding more filler, this often requires a large amount of filler, which in turn affects the mechanical properties of the silicone rubber. Summary of the Invention

[0004] The main purpose of this application is to provide a silicone rubber material and its preparation method, silicone parts, and electronic devices. This application aims to solve the problem of how to increase the density of silicone rubber material without affecting its mechanical properties.

[0005] To achieve the above objectives, this application provides a silicone rubber material, which, by mass parts, comprises: 40-100 parts of vinyl-containing siloxane, 10-50 parts of reinforcing filler, 0.001-10 parts of catalyst, 0.002-30 parts of crosslinking agent, 0.001-10 parts of inhibitor, and 1-50 parts of high-density filler.

[0006] In one embodiment, the density of the silicone rubber material is 1.2~1.8 g / cm³. 3 .

[0007] In one embodiment, the high-density filler comprises carboxylated gadolinium nanoparticles.

[0008] In one embodiment, the vinyl-containing siloxane includes at least one of methyl vinyl silicone oil, methyl phenyl vinyl silicone oil, and methyl trifluoropropyl vinyl silicone oil.

[0009] In one embodiment, the particle size of the high-density filler is 1~100 nm.

[0010] In one embodiment, the high-density filler has a shape including at least one of spherical, sheet-like, and linear shapes.

[0011] In one embodiment, the viscosity of the vinyl-containing siloxane is 10 to 1000 Pa·s.

[0012] In one embodiment, the reinforcing filler includes: silica and / or silicone resin.

[0013] In one embodiment, the catalyst comprises a platinum catalyst.

[0014] In one embodiment, the crosslinking agent comprises: hydrogen-containing silicone oil.

[0015] In one embodiment, the inhibitor includes at least one of alkynyl alcohol inhibitors, polyvinyl polysiloxane inhibitors, amide inhibitors, and maleate ester inhibitors.

[0016] To achieve the above objectives, this application provides a method for preparing a silicone rubber material, the method comprising the following steps:

[0017] A high specific gravity filler is provided, wherein the high specific gravity filler comprises: carboxylated nano-gadolinium oxide;

[0018] The reinforcing filler and the high-density filler are added to a dispersant and dispersed to obtain a slurry;

[0019] The slurry is added to a vinyl-containing siloxane and dispersed to obtain a colloid;

[0020] The catalyst, inhibitor, and crosslinking agent are added to the rubber compound and mixed, and then injection molded to obtain a silicone rubber material.

[0021] In one embodiment, the step of providing high-density filler includes:

[0022] Nano-sized gadolinium oxide is dispersed in an organic solvent to form a dispersion;

[0023] A carboxylic acid compound was added to the dispersion and refluxed to obtain carboxylated gadolinium oxide nanoparticles.

[0024] To achieve the above objectives, embodiments of this application provide a silicone component, which is made of the silicone rubber material described above, or of the silicone rubber material prepared by the preparation method described above.

[0025] To achieve the above objectives, embodiments of this application provide an electronic device, which includes the silicone component described above.

[0026] This application provides a silicone rubber material based on a vinyl-containing polysiloxane polymer, combined with reinforcing fillers, catalysts, crosslinking agents, and inhibitors, and with the addition of a small amount of high-density filler. Utilizing the high-density characteristics of the high-density filler, the density of the silicone rubber material is significantly increased, approaching the level of fluororubber. This increases the mass of the silicone rubber material, thereby enhancing the stability of silicone parts made from this material (e.g., smartwatch straps, wristbands, etc.) during wear, and giving the silicone rubber material an excellent "substantial feel." This effectively solves the problems of poor texture and lightness caused by the low density of conventional silicone rubber. Simultaneously, the addition of a small amount of high-density filler avoids the increase in hardness and decrease in elongation at break that would occur with high-part powder additions, allowing the silicone rubber material to maintain good mechanical properties. Attached Figure Description

[0027] Figure 1 This is a flowchart illustrating the method for preparing silicone rubber materials according to the embodiments of this application;

[0028] Figure 2 This is a flowchart of a high-density filler preparation method involved in the embodiments of this application.

[0029] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0031] The following detailed description, with appropriate reference to the accompanying drawings, discloses embodiments of the silicone rubber material, its preparation method, silicone parts, and electronic devices of this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of essentially identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for the purpose of enabling those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0032] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for a specific parameter, it is also expected that ranges of 60~110 and 80~120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0033] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0034] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0035] To make the above-mentioned objectives, features, and advantages of this application more apparent and understandable, the technical solution of this application is further described below in conjunction with the accompanying drawings and embodiments. However, this application is not limited to the listed embodiments, but should also include any other well-known modifications within the scope of the claims made in this application.

[0036] To better understand the technical solution of this application, a detailed description will be provided below in conjunction with the accompanying drawings and specific implementation methods.

[0037] In conventional techniques, fluororubber has a high density (1.7–1.9 g / cm³). 3Fluororubber, with its excellent mechanical strength, provides a "heavy" feel and premium texture similar to metal or ceramic, making it a common material for rubber components in wearable devices. However, fluororubber typically requires the addition of large amounts of vulcanizing agents and additives during processing, and its high-temperature vulcanization reaction easily produces irritating and corrosive gases such as hydrogen fluoride and hydrogen sulfide, which does not meet the current requirements for green environmental protection and clean production. Furthermore, fluororubber requires hot-press molding, which easily produces burrs in the molds, necessitating manual trimming after molding, resulting in low production efficiency. In contrast, silicone rubber, due to its excellent softness and elasticity and the absence of byproducts in its catalytic addition reaction, has become an ideal candidate material for wearable devices. However, conventional silicone rubber has a relatively low bulk density (typically 0.95–1.2 g / cm³). 3 This results in silicone parts that are lightweight and have a "floaty" feel, making them susceptible to displacement or wobbling under external forces during wear, affecting stability. Furthermore, they lack the "solid" or "high-end" feel required by high-end products, leading to a subjective experience of "cheapness" or "low quality." While density can be increased by adding filler, this often requires large amounts of filler (e.g., high amounts of barium sulfate and other mineral powders or metal powders), which significantly increases hardness, reduces elongation at break, decreases elasticity, makes them less wear-resistant, and more prone to breakage, making it difficult to balance high quality and comfort.

[0038] This application provides a silicone rubber material based on a vinyl-containing polysiloxane polymer, combined with reinforcing fillers, catalysts, crosslinking agents, and inhibitors, and with the addition of a small amount of high-density filler. Utilizing the high-density characteristics of the high-density filler, the density of the silicone rubber material is significantly increased, approaching the level of fluororubber. This increases the mass of the silicone rubber material, thereby enhancing the stability of silicone parts made from this material (e.g., smartwatch straps, wristbands, etc.) during wear, and giving the silicone rubber material an excellent "substantial feel." This effectively solves the problems of poor texture and lightness caused by the low density of conventional silicone rubber. Simultaneously, the addition of a small amount of high-density filler avoids the increase in hardness and decrease in elongation at break that would occur with high-part powder additions, allowing the silicone rubber material to maintain good mechanical properties.

[0039] This application provides a silicone rubber material, which, by mass parts, comprises: 40-100 parts of vinyl-containing siloxane, 10-50 parts of reinforcing filler, 0.001-10 parts of catalyst, 0.002-30 parts of crosslinking agent, 0.001-10 parts of inhibitor, and 1-50 parts of high specific gravity filler.

[0040] In one feasible embodiment, the density of the silicone rubber material is 1.2~1.8 g / cm³. 3For example, the density of silicone rubber material is 1.2 g / cm³. 3 1.25 g / cm 3 1.3 g / cm 3 1.35 g / cm 3 1.4 g / cm 3 1.45 g / cm 3 1.5 g / cm 3 1.55 g / cm 3 1.6 g / cm 3 1.65 g / cm 3 1.7 g / cm 3 1.75 g / cm 3 1.8 g / cm 3 By adjusting the proportion of high-density fillers added to silicone rubber materials, silicone rubber materials of different densities can be obtained, making the density of silicone rubber materials close to that of fluororubber, thus giving silicone rubber materials an excellent texture.

[0041] Optionally, the silicone rubber material in this application embodiment can replace fluororubber and be used to prepare silicone parts. The silicone parts can be used in electronic devices, such as wearable devices (smartwatches, smart bracelets, etc.).

[0042] Optionally, the silicone rubber material of this application embodiment can be used to manufacture the watch strap of wearable devices.

[0043] Vinyl-containing siloxanes refer to organosilicon polymers with a polysiloxane main chain (-Si-O-Si-) and vinyl groups (-CH=CH2) attached to the molecular chain. They can provide the main skeleton and flexibility of silicone rubber. At the same time, the vinyl groups (C=C) in their molecules can undergo hydrosilylation reaction with hydrogen-containing crosslinking agents under the action of catalysts to form a three-dimensional crosslinking network, thereby realizing the vulcanization (curing) of silicone rubber.

[0044] In one feasible embodiment, the vinyl-containing siloxane includes at least one of methyl vinyl silicone oil, methyl phenyl vinyl silicone oil, and methyl trifluoropropyl vinyl silicone oil.

[0045] Optionally, the amount of vinyl siloxane added to the silicone rubber material, by weight, can be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, or 100 parts, etc. As a base polymer, the appropriate amount of vinyl siloxane ensures that the silicone rubber possesses good flexibility, elongation at break, and processing flowability, while providing sufficient vinyl groups for the crosslinking reaction and ensuring the integrity of the crosslinking network. If too little vinyl siloxane is added to the silicone rubber, the polymer skeleton is insufficient, resulting in low material strength, brittleness, and inability to form an effective elastomer network. Conversely, if too much vinyl siloxane is added, the crosslinking density may be too high, restricting the movement of molecular chain segments, reducing the flexibility and elasticity of the vulcanized rubber, and even causing embrittlement. Processing flowability may also deteriorate. Therefore, in the embodiments of this application, the amount of vinyl siloxane in the rubber material is determined to be 40 to 100 parts.

[0046] In one feasible embodiment, the viscosity of the vinyl-containing siloxane is 10–1000 Pa·s. For example, the viscosities of the vinyl-containing siloxane are 10 Pa·s, 50 Pa·s, 100 Pa·s, 200 Pa·s, 300 Pa·s, 400 Pa·s, 500 Pa·s, 600 Pa·s, 700 Pa·s, 800 Pa·s, 900 Pa·s, 1000 Pa·s, etc. As a base polymer for silicone rubber, the viscosity of vinyl-containing siloxanes directly affects the processing performance, filler dispersion, and uniformity of the final product. Vinyl-containing siloxanes with a suitable viscosity of 10–1000 Pa·s can provide appropriate shear force and suspension capacity during mixing, ensuring uniform filler distribution, avoiding agglomeration, and contributing to the formation of a uniform and dense three-dimensional network structure, thereby obtaining excellent tensile strength, elongation at break, and resilience.

[0047] Optionally, the silicone rubber material includes methyl vinyl silicone oil with a viscosity of 10~1000 Pa·s.

[0048] High-density fillers are inorganic powders with a density significantly higher than that of conventional fillers. In silicone rubber materials, they can significantly increase the overall density of the material, increase the quality of the silicone rubber material, give the product a "heavy feel" and a high-end tactile experience, and effectively improve the "lightness" and poor texture problems caused by the low density of traditional silicone rubber.

[0049] In one feasible embodiment, the high-density filler comprises carboxylated gadolinium oxide nanoparticles. Gadolinium oxide (Gd₂O₃) itself has a high density (approximately 7.1 g / cm³). 3 This method can significantly increase the overall density of silicone rubber materials to 1.2–1.8 g / cm³ even at relatively low addition levels. 3The gadolinium oxide particle size is close to that of fluororubber, giving silicone parts a "substantial" feel and a premium tactile experience, improving the lightweight feel during wear. Furthermore, the nanoscale gadolinium oxide has a large specific surface area and excellent dispersion potential, thus enabling uniform distribution within the silicone rubber matrix and avoiding the agglomeration, sedimentation, and surface defects that are common with micron-sized fillers. Simultaneously, the nanoscale filler has weak visible light scattering, not affecting the transparency or coloring properties of silicone rubber, supporting various colors and appearance designs, and meeting the aesthetic requirements of high-end wearable devices. More importantly, the embodiments in this application use carboxylated nano-gadolinium oxide, whose surface contains carboxyl groups (-COOH), which can react with the Si-H bonds in the crosslinking agent: R-COOH + H-SiR'3 → R-COO-SiR'3 + H2. This allows the nano-gadolinium oxide to be stably dispersed in silicone rubber without problems such as powder migration and precipitation.

[0050] Optionally, nano-gadolinium oxide possesses high temperature and corrosion resistance, making it suitable for harsh environments, and it can also serve as a UV shielding agent. Therefore, adding it to silicone rubber materials can enhance the material's anti-aging capabilities. Furthermore, the nano-gadolinium oxide in this embodiment, after surface modification, avoids the release of free Gd. 3+ The ions are toxic to living organisms and can exist stably in silicone rubber.

[0051] Optionally, gadolinium oxide has good paramagnetism, therefore, the silicone rubber material of this application embodiment can also be used in nuclear magnetic resonance medical applications; gadolinium oxide also has good neutron shielding effect, therefore, the silicone rubber material of this application embodiment can be used to mold products that are directly in contact with the human body and have a radiation shielding effect.

[0052] Optionally, adding 20-30 wt.% carboxylated gadolinium nanoparticles to the silicone rubber material can increase the density of the silicone rubber material to 1.3-1.5 g / cm³. 3 .

[0053] Optionally, the amount of high-density filler added to the silicone rubber material, by weight, can be 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc. If the amount of high-density filler added to the silicone rubber material is too small, the density increase of the silicone rubber material will be insignificant, and the improvement in texture will be limited. If the amount of high-density filler added to the silicone rubber material is too large, the viscosity of the system will increase, the dispersion difficulty will increase, agglomeration will easily occur, and the material hardness will increase significantly, elasticity will decrease, and wearing comfort will deteriorate. However, the embodiments of this application, by adding an appropriate amount of high-density filler, can significantly increase the material density (to 1.2~1.8 g / cm³). 3 While maintaining good flexibility and elongation at break, it also maintains good flexibility and elongation at break.

[0054] In one feasible embodiment, the high-density filler has a shape including at least one of spherical, sheet-like and linear shapes.

[0055] In one feasible embodiment, the particle size of the high-density filler is 1~100 nm; for example, the particle size of the high-density filler is 1 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc. Nanoscale gadolinium oxide has a very large specific surface area and excellent dispersion potential, thus enabling uniform distribution in the silicone rubber matrix and avoiding the agglomeration, sedimentation, and surface defects that are easily caused by micron-sized fillers. Simultaneously, nanoscale fillers have weak visible light scattering, which does not affect the transparency or coloring properties of silicone rubber, supporting various colors and appearance designs, and meeting the aesthetic requirements of high-end wearable devices.

[0056] Reinforcing fillers are fine-particle inorganic powders that can significantly improve the mechanical properties of silicone rubber (such as tensile strength, tear strength, and abrasion resistance). In silicone rubber materials, they strengthen and toughen the material by limiting molecular chain slippage through physical adsorption and chemical interactions between the filler particles and polymer chains, thereby increasing the material's strength and modulus. Simultaneously, reinforcing fillers also improve the processing performance and dimensional stability of silicone rubber, making them a key component in ensuring that silicone rubber possesses practical mechanical properties.

[0057] In one feasible embodiment, the reinforcing filler includes: silica and / or silicone resin.

[0058] Optionally, silica includes fumed silica and / or precipitated silica.

[0059] Fumed silica has a small average particle size, with the average diameter of primary particles ranging from 7 to 40 nm. It also has a large specific surface area and an almost completely tightly packed three-dimensional internal structure, resulting in low hygroscopicity, strong particle surface adsorption, and a strong reinforcing effect. Silicone rubber products with added fumed silica exhibit excellent transparency, as well as good mechanical, electrical, and heat resistance properties.

[0060] Precipitated silica, due to the molecular structure of its raw material sodium silicate, exhibits numerous two-dimensional structures. Its loose structure, low molecular density, and numerous capillary structures within the aggregated state make it prone to moisture absorption, affecting its reinforcing effect. However, it possesses good resilience, compression set, and processability. Different reinforcing fillers can be selected based on the specific application requirements of silicone rubber materials.

[0061] Optionally, the amount of reinforcing filler added to the silicone rubber material, by weight, can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc. In silicone rubber materials, if the amount of reinforcing filler added is too small, the reinforcing effect will be insufficient, the material strength will be low, and it will be easily deformed, which may not meet the durability requirements of silicone parts (such as watch straps). If the amount of reinforcing filler added is too large, the viscosity of the system will increase sharply, making it difficult to mix evenly, easily causing agglomeration, and the material will harden, its elasticity will decrease, and its elongation at break will decrease significantly. The embodiments of this application, by adding an appropriate amount (10~50 parts) of reinforcing filler, significantly improve the tensile strength, tear strength, and abrasion resistance of silicone rubber, while maintaining good elasticity and processability.

[0062] The catalyst is a platinum-based catalyst used to promote hydrosilylation reactions. It can catalyze the addition reaction between vinyl-containing siloxanes and hydrogen-containing crosslinking agents, achieving rapid crosslinking and curing at room temperature or medium temperature.

[0063] In one feasible embodiment, the catalyst comprises a platinum catalyst.

[0064] Optionally, the amount of catalyst added to the silicone rubber material can be 0.001 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 5 parts, 10 parts, etc., by weight. If the amount of catalyst added is too small, the catalytic activity will be insufficient, the vulcanization speed will be too slow, the production cycle will be prolonged, and it may even lead to incomplete vulcanization, resulting in sticky products with poor strength. If there is too much catalyst filler, the reaction speed will be too fast, which may cause premature curing during injection molding, leading to material blockage and mold contamination. In this embodiment, by adding an appropriate amount of catalyst (0.001~10 parts), a rapid and uniform vulcanization reaction is achieved, ensuring that the material is fully cured in the mold and obtains good mechanical properties and surface quality.

[0065] Crosslinking agents can act as crosslinking points to undergo hydrosilylation reactions with vinyl groups in vinyl-containing siloxanes, forming -Si-CH2-CH2-Si-bridge bonds under the action of a catalyst. This connects linear polymer chains into a three-dimensional network structure, realizing the transformation from a liquid or plastic body to an elastomer.

[0066] In one feasible embodiment, the crosslinking agent includes: hydrogen-containing silicone oil.

[0067] Optionally, the crosslinking agent includes an organosilicon polymer containing Si-H groups at both ends or branch ends of the molecular chain.

[0068] Optionally, the amount of crosslinking agent added to the silicone rubber material, by weight, can be 0.002 parts, 0.005 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, etc. If the amount of crosslinking agent added is too small, there will be insufficient crosslinking points, low crosslinking density, and the material will be too soft, have poor strength, and large permanent deformation. If the amount of crosslinking agent added is too large, it may lead to over-crosslinking, making the material brittle, reducing elasticity, and decreasing elongation at break. In the embodiments of this application, by adding an appropriate amount of crosslinking agent (0.002~30 parts), sufficient crosslinking can be achieved to form a dense network, thereby obtaining ideal hardness, elasticity, and heat resistance.

[0069] Inhibitors are compounds that can reversibly regulate catalyst activity and slow down the rate of hydrosilylation reactions. They can control the reaction induction period, improve operational safety, prevent premature sulfidation (pre-curing) of the mixture during storage or processing, and ensure that the material has sufficient operating time and fluidity.

[0070] In one feasible embodiment, the inhibitor includes at least one of: alkynyl alcohol inhibitors, polyvinyl polysiloxane inhibitors, amide inhibitors, and maleate inhibitors.

[0071] Optionally, the inhibitor includes alkynol inhibitors, for example, the inhibitor includes at least one of: etynylcyclohexanol, 3-methyl-1-butyn-3-ol, 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol and diethynylacetone.

[0072] Optionally, the amount of inhibitor added to the silicone rubber material, by weight, can be 0.001 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 5 parts, 10 parts, etc. If the amount of inhibitor added is too small, the inhibition effect will be insufficient, the reaction induction period will be short, and pre-curing will easily occur, causing the mixture to gel in the pipes or molds, resulting in equipment blockage. If the amount of inhibitor added is too large, the reaction will be excessively inhibited, making it difficult to start vulcanization or resulting in incomplete vulcanization, causing the product to remain sticky after demolding, failing to meet physical properties, and potentially affecting long-term storage stability. In the embodiments of this application, by adding an appropriate amount of inhibitor (0.001~10 parts), the induction period can be effectively extended, providing sufficient operating time and fluidity, ensuring that the liquid silicone rubber does not cure prematurely before injection, and achieving stable molding.

[0073] In this embodiment, by using a vinyl-containing polysiloxane as the base polymer, combined with reinforcing fillers, catalysts, crosslinking agents, and inhibitors, and adding a small amount of high-density filler, the high-density characteristics of the high-density filler significantly increase the density of the silicone rubber material, approaching the level of fluororubber. This increases the mass of the silicone rubber material, thereby enhancing the stability of silicone parts (e.g., smartwatch straps, wristbands, etc.) made from this silicone rubber material during wear, and giving the silicone rubber material an excellent "weighty feel." This effectively solves the problems of poor texture and lightness caused by the low density of conventional silicone rubber. At the same time, by adding a small amount of high-density filler, the increase in hardness and decrease in elongation at break caused by adding a large amount of powder are avoided, allowing the silicone rubber material to maintain good mechanical properties.

[0074] This application also provides a method for preparing a silicone rubber material, used to prepare the silicone rubber material as described above, referring to... Figure 1 This includes the following steps:

[0075] Step S10: Provide a high specific gravity filler, wherein the high specific gravity filler includes: carboxylated nano-gadolinium oxide;

[0076] In one feasible embodiment, a high specific gravity filler is provided, wherein the high specific gravity filler comprises: carboxylated gadolinium nanoparticles.

[0077] In one feasible implementation, refer to Figure 2 Step S10, the step of providing high specific gravity filler includes:

[0078] Step S11: Disperse nano-gadolinium oxide in an organic solvent to form a dispersion;

[0079] In one feasible embodiment, the nano-gadolinium oxide is dried to remove water of crystallization, and then dispersed in an anhydrous organic solvent to form a dispersion.

[0080] Optionally, the organic solvent is an alcohol solvent.

[0081] Optionally, the organic solvent includes at least one of ethanol, isopropanol, and methanol.

[0082] Optionally, the nano-gadolinium oxide can be dried at 100~150 °C.

[0083] Step S12: Add a carboxylic acid compound to the dispersion and reflux the reaction to obtain carboxylated gadolinium nanoparticles.

[0084] In one feasible embodiment, a carboxylic acid compound is added to the dispersion to obtain a mixture, and the mixture is heated and refluxed to graft carboxyl groups onto the surface of the gadolinium nanoparticles. The reflux reaction temperature is 75-90 °C and the reaction time is 2-6 h. The reaction product (i.e., the carboxylated gadolinium nanoparticle solution) is subjected to solid-liquid separation, washed and dried to obtain surface-modified gadolinium nanoparticles (i.e., carboxylated gadolinium nanoparticles).

[0085] Optionally, carboxylic acid compounds include stearic acid.

[0086] In this embodiment, carboxylated nano-gadolinium oxide is prepared by carboxylating the surface of gadolinium oxide. Its surface contains carboxyl groups (-COOH), which can react with the Si-H bonds in the crosslinking agent: R-COOH + H-SiR'3 → R-COO-SiR'3 + H2. This allows the nano-gadolinium oxide to be stably dispersed in silicone rubber without problems such as powder migration and precipitation.

[0087] Step S20: Add the reinforcing filler and the high-density filler to the dispersant and disperse them to obtain a slurry;

[0088] In one feasible embodiment, 10-50 parts of reinforcing filler and 1-50 parts of high specific gravity filler are added to a dispersant and dispersed by a three-roll mill to obtain a slurry.

[0089] Optionally, the dispersant may include non-reactive silicone oil.

[0090] Optionally, the dispersant includes dimethyl silicone oil and / or vinyl silicone oil.

[0091] Optionally, the reinforcing filler includes: silica and / or silicone resin.

[0092] Step S30: The slurry is added to a vinyl-containing siloxane and dispersed to obtain a colloid;

[0093] In one feasible embodiment, the slurry is added to 40-100 parts of a vinyl-containing siloxane and dispersed by a three-roll mill to obtain a slurry.

[0094] Optionally, the vinyl-containing siloxane includes at least one of methyl vinyl silicone oil, methyl phenyl vinyl silicone oil, and methyl trifluoropropyl vinyl silicone oil.

[0095] Step S40: Add the catalyst, inhibitor and crosslinking agent to the rubber compound and mix. After injection molding, the silicone rubber material is obtained.

[0096] In one feasible embodiment, 0.001 to 10 parts of catalyst, 0.001 to 10 parts of inhibitor and 0.002 to 30 parts of crosslinking agent are added to the rubber compound, mechanically stirred, vacuum degassed, and then obtained by injection molding to obtain silicone rubber material.

[0097] Optionally, the mold temperature for injection molding is 100~180℃. For example, the mold temperature for injection molding can be 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, etc. Through efficient injection molding, silicone rubber materials can be directly made into various silicone parts. For example, watch straps can be made through injection molding; the products are burr-free, the molding process is environmentally friendly, and no toxic or harmful gases are generated.

[0098] Optionally, the silicone rubber material obtained by injection molding can be further processed according to actual needs to produce different silicone parts.

[0099] Alternatively, silicone parts can be directly produced by injection molding.

[0100] Optionally, the catalyst includes a platinum catalyst.

[0101] Optionally, the crosslinking agent includes: hydrogen-containing silicone oil.

[0102] Optionally, the inhibitor includes at least one of the following: alkynyl alcohol inhibitors, polyvinyl polysiloxane inhibitors, amide inhibitors, and maleate ester inhibitors.

[0103] In this embodiment, by using a vinyl-containing polysiloxane as the base polymer, combined with reinforcing fillers, catalysts, crosslinking agents, and inhibitors, and adding a small amount of high-density filler, the high-density characteristics of the high-density filler significantly increase the density of the silicone rubber material, approaching the level of fluororubber. This increases the mass of the silicone rubber material, thereby enhancing the stability of silicone parts (e.g., smartwatch straps, wristbands, etc.) made from this silicone rubber material during wear, and giving the silicone rubber material an excellent "weighty feel." This effectively solves the problems of poor texture and lightness caused by the low density of conventional silicone rubber. At the same time, by adding a small amount of high-density filler, the increase in hardness and decrease in elongation at break caused by adding a large amount of powder are avoided, allowing the silicone rubber material to maintain good mechanical properties.

[0104] This application also provides a silicone component, which is made of the silicone rubber material described above, or of the silicone rubber material prepared by the preparation method described above.

[0105] Optionally, silicone parts can be applied to electronic devices, such as watch straps for smartwatches and smart bracelets. This application does not limit this application.

[0106] Compared with conventional technology, the beneficial effects of the silicone parts provided in this application are the same as those of the silicone rubber materials provided in the above embodiments, and other technical features of the silicone parts are the same as those disclosed in the methods of the above embodiments, which will not be repeated here.

[0107] This application also provides an electronic device, including the silicone component described above.

[0108] Optionally, the electronic device can be a wearable device, such as a smartwatch or smart bracelet, and this application embodiment does not limit this.

[0109] Compared with conventional technology, the beneficial effects of the electronic device provided in this application embodiment are the same as the beneficial effects of the silicone rubber material provided in the above embodiment, and other technical features of the electronic device are the same as the features disclosed in the method of the above embodiment, which will not be repeated here.

[0110] In order to enable those skilled in the art to clearly understand the details and operations of the above embodiments of this application, and to demonstrate the significant improvement in performance of the embodiments of this application, the above technical solutions are illustrated below through multiple embodiments.

[0111] Example 1

[0112] (1) By mass fraction, 20 parts of fumed silica and 20 parts of carboxylated nano-gadolinium oxide were added to dimethyl silicone oil (dispersant) and dispersed by a three-roll mill to obtain a slurry;

[0113] (2) Mix the slurry, 35 parts of polyvinyl silicone oil with a viscosity of 50 Pa·s, 10 parts of polyvinyl silicone oil with a viscosity of 150 Pa·s, and 9 parts of terminal vinyl silicone oil with a viscosity of 60 Pa·s, and disperse them to obtain the adhesive.

[0114] (3) 0.1 parts of platinum catalyst, 2 parts of alkynol inhibitor and 3.9 parts of hydrogen-containing silicone oil were added to the rubber compound and mechanically stirred, vacuumed and degassed, and then injection molded to obtain silicone rubber material. The mold temperature for injection molding was 150 ℃ and the reaction time was 5 min.

[0115] The density of the silicone rubber material in Example 1 is 1.5 g / cm³. 3 Tensile strength 7 MPa, tear strength 23 N / mm.

[0116] Example 2

[0117] (1) By mass fraction, 10 parts of fumed silica and 30 parts of carboxylated nano-gadolinium oxide were added to dimethyl silicone oil (dispersant) and dispersed by a three-roll mill to obtain a slurry;

[0118] (2) Mix the slurry, 35 parts of polyvinyl silicone oil with a viscosity of 50 Pa·s, 10 parts of polyvinyl silicone oil with a viscosity of 150 Pa·s, and 9 parts of terminal vinyl silicone oil with a viscosity of 60 Pa·s, and disperse them to obtain the adhesive.

[0119] (3) 0.1 parts of platinum catalyst, 2 parts of alkynol inhibitor and 3.9 parts of hydrogen-containing silicone oil were added to the rubber compound and mechanically stirred, vacuumed and degassed, and then injection molded to obtain silicone rubber material. The mold temperature for injection molding was 150 ℃ and the reaction time was 5 min.

[0120] The density of the silicone rubber material in Example 2 is 1.8 g / cm³. 3 Tensile strength 6 MPa, tear strength 20 N / mm.

[0121] Comparative Example 1

[0122] (1) By mass fraction, 20 parts of fumed silica, 45 parts of polyvinyl silicone oil with a viscosity of 50 pa·s, 20 parts of polyvinyl silicone oil with a viscosity of 150 pa·s and 9 parts of terminal vinyl silicone oil with a viscosity of 60 pa·s are mixed and dispersed to obtain a rubber compound.

[0123] (2) 0.1 parts of platinum catalyst, 2 parts of alkynol inhibitor and 3.9 parts of hydrogen-containing silicone oil were added to the rubber compound and mechanically stirred, vacuumed and degassed, and then injection molded to obtain silicone rubber material. The mold temperature for injection molding was 150 ℃ and the reaction time was 5 min.

[0124] The density of the silicone rubber material in Comparative Example 1 is 1.1 g / cm³. 3 Tensile strength 9 MPa, tear strength 27 N / mm.

[0125] Comparative Example 2

[0126] (1) By mass fraction, 20 parts of fumed silica and 4.50 g / cm³ of silica were mixed. 3 20 parts of nano-barium sulfate filler were added to dimethyl silicone oil (dispersant) and dispersed by a three-roll mill to obtain a slurry;

[0127] (2) Mix the slurry, 35 parts of polyvinyl silicone oil with a viscosity of 50 Pa·s, 10 parts of polyvinyl silicone oil with a viscosity of 150 Pa·s, and 9 parts of terminal vinyl silicone oil with a viscosity of 60 Pa·s, and disperse them to obtain the adhesive.

[0128] (3) 0.1 parts of platinum catalyst, 2 parts of alkynol inhibitor and 3.9 parts of hydrogen-containing silicone oil were added to the rubber compound and mechanically stirred, vacuumed and degassed, and then injection molded to obtain silicone rubber material. The mold temperature for injection molding was 150 ℃ and the reaction time was 5 min.

[0129] The density of the silicone rubber material in Comparative Example 2 is 1.12 g / cm³. 3 Tensile strength 8 MPa, tear strength 18 N / mm.

[0130] Based on the test results of Examples 1 and 2 and Comparative Examples 1 and 2, it can be seen that the silicone rubber material of this application embodiment has a higher density than the conventional silicone rubber of Comparative Example 1. Therefore, it can effectively solve the problems of poor texture, lightness, and poor wearing stability caused by the low density of conventional silicone rubber. According to the experimental results of Comparative Example 2, the silicone rubber material with added nano-barium sulfate filler showed only a small increase in density and a decrease in tear strength, while the silicone rubber material of this application embodiment still maintained good tensile strength and tear strength.

[0131] The above are merely preferred embodiments of this application and do not limit the patent scope of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the patent protection scope of this application.

Claims

1. A silicone rubber material, characterized in that, The silicone rubber material comprises, by weight, 40-100 parts of vinyl-containing siloxane, 10-50 parts of reinforcing filler, 0.001-10 parts of catalyst, 0.002-30 parts of crosslinking agent, 0.001-10 parts of inhibitor, and 1-50 parts of high-density filler, wherein the high-density filler comprises carboxylated nano-gadolinium oxide, and the catalyst comprises platinum catalyst; The method for preparing the carboxylated gadolinium nanoparticles includes: Nano-sized gadolinium oxide is dispersed in an organic solvent to form a dispersion; A carboxylic acid compound was added to the dispersion and refluxed to obtain carboxylated gadolinium oxide nanoparticles. The carboxylic acid compound included stearic acid. The reflux reaction was carried out at a temperature of 75–90 °C for 2–6 h.

2. The silicone rubber material as described in claim 1, characterized in that, The density of the silicone rubber material is 1.2~1.8 g / cm³. 3 .

3. The silicone rubber material as described in claim 1, characterized in that, The vinyl-containing siloxanes include at least one of methyl vinyl silicone oil, methyl phenyl vinyl silicone oil, and methyl trifluoropropyl vinyl silicone oil.

4. The silicone rubber material as described in claim 1, characterized in that, The particle size of the high specific gravity filler is 1~100 nm; And / or, the high-density filler may have a shape including at least one of spherical, sheet-like, and linear shapes.

5. The silicone rubber material as described in claim 1 or 3, characterized in that, The viscosity of the vinyl-containing siloxane is 10~1000 Pa·s.

6. The silicone rubber material as described in claim 1, characterized in that, The reinforcing filler includes: silica and / or silicone resin; And / or, the crosslinking agent includes: hydrogen-containing silicone oil; And / or, the inhibitors include at least one of: alkynyl alcohol inhibitors, polyvinyl polysiloxane inhibitors, amide inhibitors, and maleate inhibitors.

7. A method for preparing a silicone rubber material, characterized in that, The method for preparing the silicone rubber material is used to prepare the silicone rubber material as described in any one of claims 1 to 6, and the method includes the following steps: Nano-sized gadolinium oxide is dispersed in an organic solvent to form a dispersion; A carboxylic acid compound was added to the dispersion and refluxed to obtain carboxylated gadolinium oxide nanoparticles. The carboxylic acid compound included stearic acid. The reflux reaction was carried out at a temperature of 75–90 °C for 2–6 h. The reinforcing filler and the high-density filler are added to a dispersant and dispersed to obtain a slurry; The slurry is added to a vinyl-containing siloxane and dispersed to obtain a colloid; A catalyst, an inhibitor, and a crosslinking agent are added to the rubber compound and mixed. The mixture is then injection molded to obtain a silicone rubber material. The catalyst includes a platinum catalyst.

8. A silicone part, characterized in that, The silicone component is made of silicone rubber material as described in any one of claims 1 to 6, or silicone rubber material prepared by the preparation method described in claim 7.

9. An electronic device, characterized in that, The electronic device includes the silicone component as described in claim 8.

Images