High-damping organic silicon-based composite hydrogel as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of functional composite materials, and particularly relates to high-damping organic silicon-based composite hydrogel as well as a preparation method and application thereof. The method comprises the following steps: mixing polydimethylsiloxane, silicate ester and a polyvinyl alcohol aqueous solution in proportion, and emulsifying in an ultrasonic microreactor to form an oil-in-water emulsion with specific particle size distribution. Wherein after the oil phase in the emulsion is subjected to ultrasonic action, rapid chemical crosslinking is performed to form organic silicon microspheres, and finally the organic silicon-based composite water-based damping material with the damping factor larger than 0.5 is prepared. By regulating and controlling the particle size distribution of the organic silicon microspheres, the stacking density of the microspheres in the damping material is maximized, so that the friction between the microspheres and a gel network is enhanced, and high damping is realized. The elastic composite organic silicon material has good damping performance, molding processability, recoverability and biocompatibility, raw materials are environment-friendly and low in cost, and the elastic composite organic silicon material is suitable for large-scale production and can be widely applied to the fields of flexible wearing, elastic vibration isolation, flexible protection and the like.

Description

Technical Field

[0001] This invention belongs to the field of water-based damping and impact-resistant materials, artificial skin, and shock absorption technology. More specifically, it relates to a high-damping organosilicon-based composite hydrogel, its preparation method, and its application. Background Technology

[0002] Impact-resistant and vibration-damping materials are a class of materials capable of withstanding external impacts and absorbing, dispersing, or resisting impact energy through their own physical or chemical properties, thereby reducing or preventing damage to the impacted object. These materials are widely used in modern industry and daily life, playing a crucial role in protection and vibration damping. The impact damage resistance, vibration resistance, and energy absorption capacity of high-damping materials are essential for fields such as protective materials, industrial safety, and flexible electronics. Some studies have attempted to improve the impact resistance and energy dissipation of materials. Among these, silicone-based composite materials show considerable potential for all-around protection. Compared with other elastomers, they possess unique antioxidant properties, weather resistance, and biocompatibility. These advantages have led to the widespread application of silicone rubber-based composite materials in instrumentation, biomedicine, military, aerospace, and other scientific and technological fields. However, while polydimethylsiloxane composites are the most widely used silicone products, their poor damping performance (tanδ typically less than 0.1) due to the flexibility of their chains and weak intramolecular and intermolecular interactions severely limits their practical applications. Summary of the Invention

[0003] This invention addresses the shortcomings of existing elastic organosilicon-based composite hydrogel materials in terms of poor damping performance. By introducing a polyvinyl alcohol hydrogel network into an organosilicon microsphere network with a specific particle size distribution, the frictional loss of the organosilicon elastic network during deformation is increased, thereby significantly improving the damping performance of the organosilicon material. This invention utilizes an ultrasonic microreactor and employs a mixture of hydroxyl-terminated polydimethyl silicone oil (1-10W molecular weight, 2-15% hydroxyl content), tetraethyl orthosilicate, and polyvinyl alcohol (90%-99% degree of alcoholysis) to achieve crosslinking of organosilicon under catalyst-free conditions. The resulting organosilicon emulsion is further subjected to freeze-thaw treatment to obtain a high-damping elastic organosilicon-based composite material, providing a novel, environmentally friendly, and safe preparation method with good processability. The resulting organosilicon-based composite hydrogel material exhibits excellent damping performance, recyclability, biocompatibility, and stable mechanical properties. Furthermore, the raw materials used are environmentally friendly, inexpensive, and suitable for large-scale production.

[0004] The purpose of this invention is to provide a method for preparing a high-damping organosilicon-based composite hydrogel, comprising the following steps:

[0005] S1. Mix hydroxyl-terminated polydimethylsiloxane and silicate evenly to obtain an oil phase mixture, and let it stand to remove air bubbles;

[0006] S2. Add polyvinyl alcohol to water, heat, and stir until completely dissolved to prepare an aqueous solution of polyvinyl alcohol, resulting in an aqueous mixture;

[0007] S3. Mix the oil phase mixture and the water phase mixture, slowly add the mixture dropwise into the mixing chamber of the ultrasonic generator, and emulsify and polymerize it using ultrasound to obtain an emulsion.

[0008] S4. Repeatedly freeze and thaw the emulsion to obtain a high-damping organosilicon-based composite hydrogel.

[0009] Preferably, the mass ratio of the hydroxyl-terminated polydimethylsiloxane, silicate ester, polyvinyl alcohol, and water is (5-15):(0.1-5):(1-10):(20-60); wherein the molecular weight of the hydroxyl-terminated polydimethylsiloxane is 1-10W, the hydroxyl content is 2-15%, and the degree of alcoholysis of the polyvinyl alcohol is 90%-99%.

[0010] Highly filled silicone-based composite hydrogel materials can produce waterborne damping materials with better quality and damping performance. However, single polyvinyl alcohol and single silicone rubber have significant differences in mechanical modulus, elongation at break, and storage modulus / loss modulus. The formation of silicone rubber often requires a catalyst, but catalysts such as dibutyltin dilaurate are harmful to the environment and human body. Therefore, it is very difficult to prepare biocompatible high-damping silicone-based composite hydrogels.

[0011] Preferably, the silicate ester has the following structure:

[0012] In the formula, R1, R2, and R3 are one or more of hydrogen and alkyl groups, and R4 is one or more of alkyl, γ-aminopropyl, vinyl, γ-epoxypropoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, N-(β-aminoethyl)-γ-aminopropyl, γ-methacryloyloxypropyl, γ-mercaptopropyl, chloropropyl, phenyl, ureido, and 3-trimethoxysilylpropyl.

[0013] Preferably, the hydroxyl-terminated polydimethylsiloxane is one or more of 300 cps to 10000 cps.

[0014] Preferably, the silicate ester in the component should be analytical grade with a purity > 98%; and the degree of alcoholysis of the polyvinyl alcohol should be 90%-99%.

[0015] Preferably, in step S1, the settling time is 0.1-2 hours; in step S2, the heat treatment temperature is 80-99 degrees Celsius; in step S3, the emulsification and polymerization time is 30-90 seconds, and the ultrasonic treatment power is 10-500 watts; preferably, in step S3, the ultrasonic treatment frequency is 20 kHz.

[0016] In step S4, the freeze-thaw treatment takes 5-24 hours each time.

[0017] The present invention also discloses the application of the material obtained by the above-mentioned method for preparing a high-damping organosilicon-based composite hydrogel in the preparation of impact-resistant and shock-absorbing materials.

[0018] Preferably, the hydroxyl-terminated polydimethylsiloxane is one or more of 300 cps to 10000 cps.

[0019] Preferably, the tetraethyl orthosilicate in the component should be of analytical grade with a purity > 98%.

[0020] Preferably, the degree of alcoholysis of the polyvinyl alcohol is 90%-99%. The prepared aqueous solution of polyvinyl alcohol should be 5%-15%.

[0021] Specifically, the experimental steps for preparing a high-damping organosilicon-based composite hydrogel are as follows:

[0022] S1. Prepare a 10wt% PVA aqueous solution by adding PVA to deionized water and heating to 90°C until completely dissolved, as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 minutes to remove air bubbles, as the oil phase.

[0023] S2. Draw the aqueous and oil phases into separate 50 mL syringes, connecting them to an ultrasonic microreactor (20 kHz, power 1%-100%). Driven by a syringe pump, inject the syringes containing the aqueous and oil phases into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. Set different flow rates to achieve mixing times of 90-30 s. Set different ultrasonic power levels of 10%-50%. The external operating temperature is room temperature. Different oil-in-water emulsions are obtained.

[0024] The emulsion was poured onto a 3D-printed mold and frozen at -20°C for 8-12 hours, then thawed. This freezing-thawing cycle was repeated 3-5 times to obtain an organosilicon hydrogel.

[0025] The inventors discovered in experiments that when the emulsification time of ultrasound is controlled between 30s and 90s, the components can be mixed more evenly.

[0026] The present invention has the following beneficial effects:

[0027] This invention employs a mixture of hydroxyl-terminated polydimethyl silicone oil with a molecular weight of 1-10W and a hydroxyl content of 2-15%, tetraethyl orthosilicate with a purity of >98%, and polyvinyl alcohol with a degree of alcoholysis of 90%-99%. The resulting organosilicon-based composite material exhibits excellent damping properties, processability, and biocompatibility, along with stable mechanical properties. Ultrasonic emulsification replaces traditional mechanical stirring and high-speed homogenizer emulsification. The high temperature and pressure generated locally by ultrasound lower the energy level of the reactants, eliminating the need for a catalyst and thus improving environmental protection and reducing product costs. Furthermore, the microstructure of the prepared organosilicon rubber is controlled. Different sphere sizes allow for varying filling system distributions, increasing the friction of the microspheres' specific surface area within the internal structure, thus improving energy dissipation and achieving high damping performance in the material. Adding hydroxyl silicone oil with appropriate hydroxyl content and adjusting the ratio of hydroxyl silicone oil to tetraethyl orthosilicate, followed by emulsification in a polyvinyl alcohol aqueous solution of a certain concentration, causes the tetraethyl orthosilicate to hydrolyze. The localized high temperature and pressure of ultrasound drive the reaction between polydimethylsiloxane and tetraethyl orthosilicate, forming microspheres. After freeze-thaw cycles, these microspheres polymerize in situ with polyvinyl alcohol, forming a high-damping organosilicon-based hydrogel composite material. Furthermore, all raw materials used are environmentally friendly, inexpensive, and suitable for large-scale production. Attached Figure Description

[0028] Figure 1 Images showing the organosilicon-based hydrogel emulsion and its particle size distribution obtained in Example 1;

[0029] Figure 2 Image of the silicone-based hydrogel emulsion obtained in Example 2;

[0030] Figure 3 Image of the silicone-based hydrogel emulsion obtained in Example 3;

[0031] Figure 4 Images showing the particle size distribution of the silicone-based hydrogel emulsion obtained in Example 4;

[0032] Figure 5 Image showing the particle size distribution of the silicone-based hydrogel emulsion obtained in Example 5;

[0033] Figure 6 Image showing the particle size distribution of the silicone-based hydrogel emulsion obtained in Example 6;

[0034] Figure 7 Image showing the particle size distribution of the silicone-based hydrogel emulsion obtained in Example 7;

[0035] Figure 8 Image showing the particle size distribution of the silicone-based hydrogel emulsion obtained in Example 8;

[0036] Figure 9 Image showing the particle size distribution of the silicone-based hydrogel emulsion obtained in Example 9;

[0037] Figure 10 The image shows the effect of particle size distribution of the silicone-based hydrogel emulsion obtained in Example 10 on its damping performance.

[0038] Figure 11 Images showing the recyclability of the silicone-based hydrogel obtained in Example 11;

[0039] Figure 12 Images showing the biocompatibility of the silicone-based hydrogel obtained in Example 12;

[0040] Figure 13 Images of the silicone-based hydrogel emulsion obtained in Comparative Example 1 and its performance testing.

[0041] Figure 14 Images of the silicone-based hydrogel emulsion obtained in Comparative Example 2 and its performance testing.

[0042] Figure 15 Images of the silicone-based hydrogel emulsion obtained in Comparative Example 3 and its performance testing.

[0043] Figure 16 Images of the silicone-based hydrogel emulsion obtained in Comparative Example 4 and its performance testing. Detailed Implementation

[0044] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0045] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0046] The amount of each component added is calculated in parts by weight.

[0047] Example 1: Preparation of a high-damping silicone-based hydrogel emulsion (oil phase mixture ratio 5:1)

[0048] (1) Preparation of aqueous and oil phases

[0049] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0050] (2) Emulsification process

[0051] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-to-aqueous mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 3.4 mL / min, and the mixing time to 60 s. Different ultrasonic powers were set, such as 10% (for A1 unimodal particle size distribution emulsion) (5-13 W), 20% (for B1 bimodal particle size distribution emulsion) (62-69 W), 30% (for B2 bimodal particle size distribution emulsion) (115 W-120 W), 40% (for B3 bimodal particle size distribution emulsion) (180 W-189 W), and 50% (for A2 unimodal particle size distribution emulsion) (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0052] Example 2: Preparation of a high-damping silicone-based hydrogel emulsion (oil phase mixture ratio 2:1)

[0053] (1) Preparation of aqueous and oil phases

[0054] Prepare a 10 wt% aqueous solution of PVA (type 124) as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 2:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0055] (2) Emulsification process

[0056] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 3.4 mL / min, and the mixing time to 60 s. Different ultrasonic powers were set, such as 10% (5-13 W), 20% (62-69 W), 30% (115 W-120 W), and 40% (180 W-189 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0057] (The emulsion is unstable, making it impossible to measure particle size)

[0058] Example 3: Preparation of a high-damping silicone-based hydrogel emulsion (oil phase mixture ratio 10:1)

[0059] (1) Preparation of aqueous and oil phases

[0060] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 10:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0061] (2) Emulsification process

[0062] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-to-aqueous mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 3.4 mL / min, and the mixing time to 60 s. Different ultrasonic powers were set, such as 10% (5-13 W), 20% (62-69 W), 30% (115 W-120 W), 40% (180 W-189 W), and 50% (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained. (The emulsions were unstable, and particle size could not be measured.)

[0063] Example 4: Preparation of a high-damping silicone-based hydrogel emulsion (ultrasonic power 10%)

[0064] (1) Preparation of aqueous and oil phases

[0065] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0066] (2) Emulsification process

[0067] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. Flow rates were set to 1.7, 3.4, and 6.8 mL / min, with mixing times of 90 s, 60 s, and 30 s, respectively. The ultrasonic power was set to 10% (5-13 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0068] Example 5: Preparation of a high-damping silicone-based hydrogel emulsion (ultrasonic power 30%)

[0069] (1) Preparation of aqueous and oil phases

[0070] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0071] (2) Emulsification process

[0072] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. Flow rates were set to 1.7, 3.4, and 6.8 mL / min, with mixing times of 90 s, 60 s, and 30 s, respectively. The ultrasonic power was set to 30% (115 W-120 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0073] Example 6: Preparation of a high-damping silicone-based hydrogel emulsion (ultrasonic power 50%)

[0074] (1) Preparation of aqueous and oil phases

[0075] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0076] (2) Emulsification process

[0077] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. Flow rates were set to 1.7, 3.4, and 6.8 mL / min, with mixing times of 90 s, 60 s, and 30 s, respectively. The ultrasonic power was set to 50% (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0078] Example 7: Preparation of a high-damping silicone-based hydrogel emulsion (ultrasound time: 30 s)

[0079] (1) Preparation of aqueous and oil phases

[0080] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0081] (2) Emulsification process

[0082] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 6.8 mL / min, and the mixing time to 30 s. The ultrasonic power was set to 10% (5-13 W), 20% (62-69 W), 30% (115 W-120 W), 40% (180 W-189 W), and 50% (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0083] Example 8: Preparation of a high-damping silicone-based hydrogel emulsion (ultrasound time: 60 s)

[0084] (1) Preparation of aqueous and oil phases

[0085] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0086] (2) Emulsification process

[0087] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-to-aqueous mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 3.4 mL / min, and the mixing time to 60 s. The ultrasonic power was set to 10% (5-13 W), 20% (62-69 W), 30% (115 W-120 W), 40% (180 W-189 W), and 50% (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0088] Example 9: Preparation of a high-damping silicone-based hydrogel emulsion (ultrasound time: 90 s)

[0089] (1) Preparation of aqueous and oil phases

[0090] Prepare a 10wt% PVA (type 1799) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0091] (2) Emulsification process

[0092] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 1.7 mL / min, and the mixing time to 90 s. The ultrasonic power was set to 10% (5-13 W), 20% (62-69 W), 30% (115 W-120 W), 40% (180 W-189 W), and 50% (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0093] Example 10: Preparation of high-damping silicone-based composite materials (Influence of different particle sizes on damping performance)

[0094] (1) Preparation of aqueous and oil phases

[0095] Prepare a 10wt% PVA (type 1799) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0096] (2) Emulsification process

[0097] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 6.8 mL / min, and the mixing time to 30 s. The ultrasonic power was set to 10% (5-13 W), 20% (62-69 W), 30% (115 W-120 W), 40% (180 W-189 W), and 50% (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0098] (3) Molding

[0099] The emulsion was poured into a mold and frozen at -20°C for 12 hours, then thawed. This freezing-thawing cycle was repeated three times to obtain the silicone hydrogel.

[0100] Example 11: Recyclability of High-Damping Organosilicon-Based Composite Materials

[0101] The emulsion was poured into a mold and frozen at -20°C for 12 hours, then thawed. This freezing-thawing cycle was repeated three times to obtain an organosilicon hydrogel. This hydrogel was then added to a small amount of deionized water and heated to above 90°C, where it redissolved as an emulsion.

[0102] Example 12 Biocompatibility of High Damping Organosilicon-Based Composite Materials

[0103] The emulsion was poured onto a mold and frozen at -20°C for 12 hours, then thawed. This freezing-thawing cycle was repeated three times to obtain the silicone hydrogel. The silicone hydrogel was then placed in an agar plate coated with E. coli using the plate-coating method. After 48 hours, an inhibition zone was observed.

[0104] Comparative Example 1: Preparation of high-damping organosilicon-based composite material (the viscosity of the silicone oil in the oil phase is 500 cps).

[0105] (1) Preparation of aqueous and oil phases

[0106] Prepare a 10 wt% PVA (type 1799) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 500 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0107] (2) Emulsification process

[0108] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-to-aqueous mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 3.4 mL / min, and the mixing time to 60 s. Different ultrasonic powers were set, such as 10% (5-13 W), 20% (62-69 W), 30% (115 W-120 W), 40% (180 W-189 W), and 50% (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0109] (3) Molding

[0110] The emulsion was poured into a mold and frozen at -20°C for 12 hours, then thawed. This freezing-thawing cycle was repeated three times to obtain the silicone hydrogel.

[0111] The only difference from Example 10 is that in step (1), the viscosity of the hydroxyl silicone oil is 500 cps.

[0112] The organosilicon-based hydrogel obtained in Comparative Example 1 is as follows: Figure 11 As shown: Organosilicon-based hydrogel emulsions are unstable, have a uniform particle size distribution, and exhibit poor damping performance.

[0113] Comparative Example 2: Preparation of high-damping organosilicon-based composite material (tetraethyl orthosilicate in the oil phase mixture was replaced with tris(2-methoxyethoxy)vinylsilane)

[0114] (1) Preparation of aqueous and oil phases

[0115] Prepare a 10 wt% aqueous solution of PVA (type 124) as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tris(2-methoxyethoxy)vinylsilane at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0116] (2) Emulsification process

[0117] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-to-aqueous mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. The flow rate was set to 3.4 mL / min, and the mixing time to 60 s. Different ultrasonic powers were set, such as 10% (5-13 W), 20% (62-69 W), 30% (115 W-120 W), 40% (180 W-189 W), and 50% (251 W-280 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0118] (3) Molding

[0119] The emulsion was poured into a mold and frozen at -20°C for 12 hours, then thawed. This freezing-thawing cycle was repeated three times to obtain the silicone hydrogel.

[0120] The only difference from Example 10 is that in step (1), the silane coupling agent is tris(2-methoxyethoxy)vinylsilane.

[0121] The properties of the organosilicon-based hydrogel obtained in Comparative Example 2 are as follows: Figure 12 As shown: the particle size distribution is uniform, and the damping performance is poor.

[0122] Comparative Example 3: Preparation of a high-damping silicone-based hydrogel emulsion (ultrasonic power 20%)

[0123] 1) Preparation of aqueous and oil phases

[0124] Prepare a 10wt% PVA (type 1799) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0125] (2) Emulsification process

[0126] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. Flow rates were set to 1.7, 3.4, and 6.8 mL / min, with mixing times of 90 s, 60 s, and 30 s, respectively. The ultrasonic power was set to 20% (62 W-69 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0127] (3) Molding

[0128] The emulsion was poured into a mold and frozen at -20°C for 12 hours, then thawed. This freezing-thawing cycle was repeated three times to obtain the silicone hydrogel.

[0129] Comparative Example 4: Preparation of a high-damping silicone-based hydrogel emulsion (ultrasonic power 40%)

[0130] 1) Preparation of aqueous and oil phases

[0131] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0132] (2) Emulsification process

[0133] The aqueous and oil phases were separately drawn into 50 mL syringes and connected to an ultrasonic emulsifier (20 kHz, power 1%-100%). Driven by a syringe pump, the syringes containing the oil-water mixture were injected into the mixing chamber of the ultrasonic generator at a volume ratio of 4:1. Flow rates were set to 1.7, 3.4, and 6.8 mL / min, with mixing times of 90 s, 60 s, and 30 s, respectively. The ultrasonic power was set to 40% (180 W-189 W). The operating temperature was room temperature. Different oil-in-water emulsions were obtained.

[0134] (3) Molding

[0135] The emulsion was poured into a mold and frozen at -20°C for 12 hours, then thawed. This freezing-thawing cycle was repeated three times to obtain the silicone hydrogel.

[0136] Comparative Example 5: Preparation of High-Damping Silicone-Based Hydrogel Emulsion (High-Speed ​​Homogenization Method)

[0137] 1) Preparation of aqueous and oil phases

[0138] Prepare a 10 wt% PVA (type 124) aqueous solution as the aqueous phase. Mix hydroxyl-terminated polydimethylsiloxane (PDMS, 1000 cps) prepolymer and tetraethyl orthosilicate (TEOS, AR) at a mass ratio of 5:1. After thorough stirring, let stand at room temperature for 30 min to remove air bubbles, and this mixture will be the oil phase.

[0139] (2) Emulsification process

[0140] Pour the aqueous phase and oil phase into 100mL beakers respectively, and emulsify them using a high-speed homogenizer.

[0141] (3) Molding

[0142] The emulsion was poured into a mold and frozen at -20°C for 12 hours, then thawed. This freezing-thawing cycle was repeated three times; an oil phase mixture flowed out, but the emulsion did not solidify.

[0143] Table 1. Formulation of High Damping Organosilicon-Based Composite Materials (Unit: g)

[0144]

[0145]

[0146] Table 2 Emulsification conditions and emulsion properties

[0147]

[0148] Table 3 Experimental conditions and material properties

[0149] Example 10 Damping performance tan& Elongation at break Fatigue resistance Extreme strain 10％ 0.09 172％ >1000 times 60％ 20％ 0.12 184％ >1000 times 60％ 30％ 0.51 213％ >1000 times 70％ 40％ 0.31 209％ >1000 times 50％ 50％ 0.14 179％ >1000 times 50％

[0150] Table 4 Comparative Emulsion Properties and Material Properties

[0151] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 polydimethylsiloxane 500cps 1000cps 1000cps 1000cps 1000cps Coupling agent Tetraethyl orthosilicate A-172 Tetraethyl orthosilicate Tetraethyl orthosilicate Tetraethyl orthosilicate Preparation method ultrasound ultrasound ultrasound ultrasound High-speed homogenization emulsion state Unstable Unstable Stablize Stablize Unstable Molding state forming forming forming forming Unformed Damping performance tan& ＜0.05 ＜0.05 0.12 0.31 0

[0152] As can be seen from the data in Table 1, the ratio of polydimethylsiloxane to tetraethyl orthosilicate in the oil phase mixture was explored in Examples 1-3. From the emulsion state and particle size distribution, it can be seen that the emulsion is most stable when the ratio of polydimethylsiloxane to tetraethyl orthosilicate in the oil phase mixture is 5:1.

[0153] As can be seen from the data in Table 2, Examples 4-9 explored the effects of different ultrasonic emulsification powers and different ultrasonic emulsification times on particle size distribution. When the ultrasonic power was 10% and 50%, the emulsion particle size distribution showed a single-peak distribution, while at 30%, the emulsion particle size distribution showed a double-peak distribution.

[0154] As can be seen from the data in Table 3, Example 10 explored the performance of hydrogels prepared under ultrasonic emulsification power of 10%-50% after molding. It can be seen that the organosilicon-based hydrogel with bimodal particle size distribution prepared under 30% power has the best damping performance, and its other properties are also slightly better than others.

[0155] As can be seen from the data in Table 4, Comparative Examples 1-5 explored the effects of the viscosity of polydimethylsiloxane, the type of silane coupling agent, 20% ultrasonic power, 40% ultrasonic power, and different preparation methods on the material properties.

[0156] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a high-damping organosilicon-based composite hydrogel, characterized in that... It includes the following steps: S1. Mix hydroxyl-terminated polydimethylsiloxane and silicate evenly to obtain an oil phase mixture, and let it stand to remove air bubbles; S2. Add polyvinyl alcohol to water, heat, and stir until completely dissolved to prepare an aqueous solution of polyvinyl alcohol, resulting in an aqueous mixture; S3. Mix the oil phase mixture and the water phase mixture, slowly add the mixture dropwise into the mixing chamber of the ultrasonic generator, and emulsify and polymerize it using ultrasound to obtain an emulsion. S4. Repeatedly freeze and thaw the emulsion to obtain a high-damping organosilicon-based composite hydrogel.

2. The method for preparing a high-damping organosilicon-based composite hydrogel according to claim 1, characterized in that, The mass ratio of the hydroxyl-terminated polydimethylsiloxane, silicate ester, polyvinyl alcohol, and water is (5-15):(0.1-5):(1-10):(20-60); wherein the molecular weight of the hydroxyl-terminated polydimethylsiloxane is 1-10W, the hydroxyl content is 2-15%, the degree of polymerization of the polyvinyl alcohol is 1000-3000, and the degree of alcoholysis is 90%-99%.

3. The method for preparing a high-damping organosilicon-based composite hydrogel according to claim 1, characterized in that, The silicate ester has the following structure: In the formula, R1, R2, and R3 are one or more of hydrogen and alkyl groups, and R4 is one or more of alkyl, γ-aminopropyl, vinyl, γ-epoxypropoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, N-(β-aminoethyl)-γ-aminopropyl, γ-methacryloyloxypropyl, γ-mercaptopropyl, chloropropyl, phenyl, ureido, and 3-trimethoxysilylpropyl.

4. The method for preparing a high-damping organosilicon-based composite hydrogel according to claim 1, characterized in that, The hydroxyl-terminated polydimethylsiloxane is one or more of the range of 300 cps to 10000 cps.

5. The method for preparing a high-damping organosilicon-based composite hydrogel according to claim 1, characterized in that, The silicate ester in the components should be analytical grade with a purity > 98%; the degree of alcoholysis of the polyvinyl alcohol should be 90%-99%.

6. The method for preparing the high-damping organosilicon-based composite hydrogel according to claim 1, characterized in that, In step S1, the settling time is 0.1-2 hours; in step S2, the heating temperature is 80-99 degrees Celsius; in step S3, the emulsification and polymerization time is 30-90 seconds, the ultrasonic treatment power is 10-500 watts, and the ultrasonic treatment frequency is 5-50 kHz; in step S4, the freeze-thaw treatment time is 5-24 hours each time.

7. The high-damping organosilicon-based composite hydrogel prepared by the preparation method of any one of claims 1 to 6.

8. The application of the material obtained by the preparation method of the high-damping organosilicon-based composite hydrogel according to any one of claims 1 to 6 in the preparation of impact-resistant, shock-absorbing materials and artificial skin.

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