A boron-containing resin type wide-temperature-range damping additive, a preparation method and application thereof

Abstract

The application relates to a boron-containing resin type wide-temperature-range damping additive and a preparation method and application thereof, and belongs to the technical field of organic silicon damping materials. The boron-containing resin type wide-temperature-range damping additive comprises: A) an organic silicon resin matrix with a three-dimensional network structure; B) a boron-containing functional structure connected with the organic silicon resin matrix; and C) an aryl-containing functional structure connected with the organic silicon resin matrix. The boron-containing functional structure is connected to the surface of the three-dimensional network structure of the organic silicon resin matrix through a Si-O-B bond; the aryl-containing functional structure is located on the surface of the three-dimensional network structure of the organic silicon resin matrix; the molecular weight of the organic silicon resin matrix is 1000-10000; and the organic silicon resin matrix is selected from one or more of MQ resin, MT resin, MTQ resin, MDT resin and POSS silicon resin. The application improves the high-temperature dissipation capacity and wide-temperature-range damping performance of the damping material through the synergistic effect of the rigid silicon resin and the surface boron-containing dynamic structure, and takes into account the compatibility and mechanical stability.

Description

Technical Field

[0001] This application relates to a boron-containing resin-based wide-temperature-range damping additive, its preparation method, and its application, belonging to the technical field of organosilicon damping materials. Background Technology

[0002] With the rapid development of deep space exploration technology, the service environment faced by spacecraft and their onboard equipment is becoming increasingly harsh and complex. The equipment must withstand drastic temperature changes from the extremely cold shadow regions of extraterrestrial bodies to the high-temperature regions of near-solar orbits. These extreme conditions pose unprecedented challenges to the performance of damping materials. Damping materials must possess an ultra-wide effective damping temperature range to ensure the structural stability of the spacecraft, the accuracy of the instruments, and the safety of service.

[0003] The backbone of silicone rubber has a -Si-O-Si- structure, unlike the -CC- backbone of ordinary rubber. Silicone rubber has longer bond lengths and larger bond angles, giving it extremely high flexibility and a lower internal rotational barrier, allowing chain segments to move even at very low temperatures. Furthermore, the bond energy of the Si-O bonds in the silicone rubber backbone is higher than that of the CC bonds, resulting in better high-temperature resistance. However, the excessive flexibility of the silicone rubber molecular chains leads to the failure of energy dissipation mechanisms at high temperatures. At high temperatures, the mobility of the silicone rubber molecular chains is significantly enhanced, and the chain segments respond rapidly to external forces, almost synchronously with changes in force. This results in less internal friction, less energy dissipation, and poor damping performance. Therefore, to meet the urgent need for wide-temperature-range damping in the complex conditions of deep space, modifying silicone rubber to broaden its effective damping temperature range, especially improving its energy dissipation capacity at high temperatures, has become a crucial research topic in the field of polymer materials.

[0004] To overcome this limitation, modern damping material design emphasizes the synergistic effect of multiple energy dissipation mechanisms. Compared to materials with a single mechanism, damping materials with multiple energy dissipation mechanisms can cover a wider temperature range through relaxation processes of different mechanisms, significantly broadening the material's loss peak. They can even form multiple loss peaks in different temperature ranges, allowing the material to maintain high damping performance across a wide range from low to high temperatures and from low to high frequencies. Dynamic bonds refer to chemical bonds or interactions that can undergo reversible breakage and recombination under specific conditions, endowing polymer materials with unique dynamic properties. Under stress, the dynamic bonds within the material can break and recombine. During the breakage process, energy is absorbed and energy is lost, providing a certain degree of damping performance to the polymer material. As dynamic cross-linking points between molecular chains, the breakage and recombination of dynamic bonds allow for a certain degree of relative slippage between molecular chains, generating significant internal friction and further increasing energy dissipation.

[0005] Chinese patent CN119899386B discloses a polyborosiloxane-type damping additive for phenyl silicone rubber. The system used in this design is essentially a flexible linear polysiloxane dynamic system, with its main structure consisting of polysiloxane segments. The boron-oxygen dynamic bonds are primarily distributed within the flexible chain structure, and energy dissipation mainly relies on dynamic bond exchange and relative segment slippage. Chinese patent CN117903435B discloses an MQ resin-type silicone rubber damping additive. It utilizes the sterically hindered phenyl groups in the silicone resin to increase internal friction in the silicone rubber, thereby improving the high-temperature damping performance of the composite material. The polyborosiloxane system in Chinese patent CN119899386B and the organosilicon resin system in Chinese patent CN117903435B differ significantly in molecular structure and energy dissipation mode.

[0006] Polyborosiloxanes typically belong to flexible linear polysiloxane systems, with their main structure consisting of linear Si-O-Si segments and dynamic boron-oxygen bonds primarily distributed between the flexible polysiloxane chains. In these systems, the molecular chains exhibit high degrees of freedom, and the dynamic boron-oxygen bonds can undergo reversible breakage and recombination during chain segment movement. Energy dissipation mainly relies on dynamic bond exchange and relative segment slippage. Organosilicon resin systems, on the other hand, typically possess a three-dimensional network structure. Their molecular structure contains numerous high-functionality silicon-oxygen structural units, capable of forming spatially branched or cage-like silicon-oxygen networks. Compared to flexible linear polysiloxanes, organosilicon resin systems have a denser network structure, greater steric hindrance, and significantly restricted chain segment movement, resulting in stronger network confinement effects and interfacial constraints within the material. This leads to significant differences in the dynamic structural behavior, stress transmission mechanisms, and energy dissipation mechanisms of resin-type silicon-oxygen networks compared to polyborosiloxane systems.

[0007] For organosilicon resin systems with highly three-dimensional silica-oxygen network structures, the introduction of dynamic structures into the resin network can easily lead to gelation, structural runaway, or dynamic structure failure due to the dense network structure, large steric hindrance, and sensitivity to condensation reactions. Therefore, it remains uncertain whether dynamic boron-oxygen structures are equally applicable to resin-type silica-oxygen network systems. Furthermore, a search revealed no reports in the prior art of introducing dynamic boron-oxygen bonds into resin-type silica-oxygen networks to construct wide-temperature-range damping systems. In addition, whether introducing resin-type silica-oxygen networks can maintain resin network stability and successfully construct effective dynamic dissipation structures remains an important problem that is still uncertain in this field and urgently needs to be studied and solved.

[0008] It should be noted that the above content is used to illustrate the research and development ideas of this application and does not necessarily constitute prior art. Summary of the Invention

[0009] This application provides a boron-containing resin-type wide-temperature-range damping additive, its preparation method, and its application. For the first time, a dynamic boron-oxygen structure is introduced into the surface of an organosilicon resin with a three-dimensional network structure, constructing a resin-type dynamic dissipation structure that is different from the flexible linear polysiloxane system. This achieves the synergistic effect of multiple energy dissipation mechanisms, such as dynamic boron-oxygen bond dissipation and π-π interactions between aryl groups. While maintaining the stability and mechanical properties of the resin network, this improves the high-temperature damping performance of the material and broadens the effective damping temperature range.

[0010] Adding this damping additive to high-temperature vulcanized silicone rubber can produce a composite material with high mechanical strength and high damping performance, achieving a significant performance improvement compared to existing technologies and meeting more stringent and complex application scenarios.

[0011] This application provides a boron-containing resin-based wide-temperature-range damping additive, wherein the boron-containing resin-based wide-temperature-range damping additive comprises: A) An organosilicon resin matrix with a three-dimensional network structure; B) A boron-containing functional structure connected to the silicone resin matrix; C) An aryl-containing functional structure connected to the organosilicon resin matrix; The boron-containing functional structure is connected to the surface of the three-dimensional network structure of the organosilicon resin matrix via Si-OB bonds; the aryl-containing functional structure is located on the surface of the three-dimensional network structure of the organosilicon resin matrix. The molecular weight of the organosilicon resin matrix is ​​1000~10000.

[0012] Organosilicon resins are semi-inorganic and semi-organic polymers with -Si-O- as the main chain and organic groups linked to the side chains. They are highly cross-linked, three-dimensional network structures of polyorganosiloxanes. Boron-containing functional structures are groups containing boron, with at least one boron group linked to the surface of the three-dimensional network structure of the organosilicon resin matrix via Si-OB bonds, serving as the end-capping structure of the organosilicon resin matrix. Aryl-containing functional structures are groups containing aryl groups, which are linked to the surface of the three-dimensional network structure of the organosilicon resin matrix, serving as the end-capping structure of the organosilicon resin matrix.

[0013] In this application, the molecular weight of the silicone resin matrix is ​​controlled between 1000 and 10000. When the molecular weight is too low, the branching degree and network size of the silicone resin matrix are small, resulting in insufficient resin network confinement and difficulty in forming a stable and effective multiple energy dissipation structure. Simultaneously, the interfacial interaction between the low molecular weight resin and the silicone rubber system is weak, easily leading to insufficient dynamic structure dissipation capacity and limited improvement in damping performance. When the molecular weight of the silicone resin matrix is ​​too high, the resin network size and intermolecular interactions increase significantly, but the solubility and dispersibility of the system decrease, making it prone to local aggregation in the silicone rubber system. This results in uneven distribution of the dynamic boron-oxygen structure, limiting the dynamic structure exchange capacity and interfacial dissipation behavior.

[0014] Meanwhile, excessively high molecular weight can lead to decreased processing fluidity of the system, which is not conducive to the formation of a uniform and stable resin-type dynamic dissipation structure, thus affecting the wide-temperature-range damping performance and mechanical stability of the material. However, controlling the molecular weight of the organosilicon resin matrix within the range of 1000 to 10000 is beneficial to balance the resin network confinement effect, system solubility and dispersibility, and dynamic structural exchange capacity, thereby forming a stable and uniform multi-energy dissipation system.

[0015] Optionally, the silicone resin matrix is ​​selected from one or more of MQ resin, MT resin, MTQ resin, MDT resin, and POSS silicone resin. MQ resin, MT resin, MTQ resin, MDT resin, and POSS silicone resin are all silicone resins well known to those skilled in the art. For example, M represents a monofunctional linker, D represents a difunctional linker, T represents a trifunctional linker, and Q represents a tetrafunctional linker. POSS silicone resin is short for polyoctahedral silsesquioxanes, also known as polyhedral silsesquioxane or cage-type polysesquioxane.

[0016] It should be noted that the above-listed examples are only common silicone resin matrices. The solutions in this application are not limited to the silicone resins listed above. Those skilled in the art can achieve the same technical effects by using the solutions in this application based on the content described herein.

[0017] Optionally, the aryl-containing functional structure is formed on the surface of the three-dimensional network structure of the organosilicon resin matrix as an aryl-containing M unit with the following structure: R1, R2, and R3 are each independently selected from aryl and alkyl groups, and at least one of R1, R2, and R3 is aryl.

[0018] Optionally, the aryl group is phenyl or biphenyl.

[0019] Optionally, the alkyl group is a C1 to C6 alkyl group.

[0020] Optionally, the boron-containing functional structure is selected from one or more of the following structures: .

[0021] It should be noted that the preparation process of the boron-containing resin-type wide-temperature-range damping additive is not limited in this application. For example, an aryl functional structure can be introduced into the silicone resin matrix first, followed by a boron-containing functional structure; or a boron-containing functional structure can be introduced into the silicone resin matrix first, followed by an aryl functional structure; or a boron-containing functional structure and an aryl functional structure can be introduced simultaneously in a one-step reaction; or the process can be flexibly adjusted, for example, by repeatedly introducing the boron-containing functional structure and the aryl functional structure separately or simultaneously in multiple stages.

[0022] For example, this application provides a specific preparation process that first introduces an aryl functional structure into an organosilicon resin matrix, and then introduces a boron functional structure. Specifically, the process for preparing an organosilicon resin matrix containing an aryl functional structure as described in the prior Chinese patent CN117903435B can be used, or commercially available products that meet the requirements can be used directly, or other processes that can prepare structures that meet the requirements of this application can be used.

[0023] In one specific approach, an organosilicon resin matrix with an aryl functional structure on its surface is directly used. The residual hydroxyl groups on the surface react with boron-containing compounds to further introduce boron-containing functional structures. The organosilicon resin matrix with the aryl functional structure on its surface can be one or more of monophenyl silicone resin, diphenyl silicone resin, and triphenyl silicone resin.

[0024] For monophenyl silicone resins, the representative is the aryl M unit: Of R1, R2, and R3, only one is aryl.

[0025] For diphenyl silicone resin, the representative is the aryl M unit: Of the three compounds R1, R2, and R3, only two are aryl.

[0026] For triphenylsilane resin, the representative is the aryl M unit: In this case, R1, R2, and R3 are all aryl groups.

[0027] This application provides a method for preparing the above-mentioned boron-containing resin-type wide-temperature-range damping additive, comprising the following steps: Mix an organosilicon resin matrix with an aryl functional structure on its surface with an organic solvent; Add boron-containing compounds and mix thoroughly; The heating reaction yields a crude product of a boron-containing resin-type wide-temperature-range damping additive. After purification, a boron-containing resin-type wide-temperature-range damping additive was obtained.

[0028] In this application, the silicone resin matrix with an aryl functional structure on its surface can be prepared by referring to the method in Chinese Patent CN117903435B, but is not limited to the method in Chinese Patent CN117903435B. Those skilled in the art can prepare a silicone resin matrix with an aryl functional structure on its surface based on its disclosure and basic experimental capabilities, for example, by using materials such as MQ resin, MT resin, MTQ resin, MDT resin, POSS silicone resin, etc., but not limited to the above-mentioned silicone resin matrix, to prepare a silicone resin matrix with an aryl functional structure on its surface.

[0029] A silicone resin with a three-dimensional network structure is formed through the hydrolysis and condensation of aryl silane monomers, resulting in the formation of aryl functional structures on the resin surface. Since some silanol groups are not completely condensed during the silicone resin polymerization process, a certain amount of active Si-OH groups are typically retained on the resin surface. Subsequently, the silicone resin matrix with the aryl functional structure on its surface is mixed with a boron-containing compound in an organic solvent and heated for reaction. The Si-OH groups on the resin surface can undergo dehydration condensation with the hydroxyl groups in the boron-containing compound, forming a Si-OB linkage structure on the silicone resin surface, thus obtaining a boron-containing resin-type wide-temperature-range damping additive. The resulting boron-containing structure is mainly distributed on the surface of the resin-type silicon-oxygen network. By introducing a dynamic boron-oxygen structure while retaining the three-dimensional branched network structure of the silicone resin, a resin-type dynamic dissipation system with multiple energy dissipation capabilities is formed.

[0030] Optionally, the ratio of hydroxyl groups in the silicone resin matrix with aryl functional structures to those in the boron-containing compound is 1:(0.5~2). If this hydroxyl group ratio is too high, it indicates that the amount of boron-containing compound added is too low, which leads to a reduction in the amount of boron introduced, resulting in a poorer improvement in damping performance of the prepared additive product. If the hydroxyl group ratio is too low, it indicates that the amount of boron-containing compound introduced is insufficient, leaving more hydroxyl groups in the silicone resin matrix, which leads to a deterioration in the mechanical properties of the final composite rubber material product.

[0031] Optionally, the ratio of the hydroxyl groups of the organosilicon resin matrix with aryl functional structure to the hydroxyl groups of the boron-containing compound on the surface is 1:(1.0~2).

[0032] Optionally, the ratio of the hydroxyl groups of the organosilicon resin matrix with aryl functional structure to the hydroxyl groups of the boron-containing compound on the surface is 1:(1.2~2).

[0033] Optionally, the ratio of the hydroxyl groups of the organosilicon resin matrix with aryl functional structure to the hydroxyl groups of the boron-containing compound on the surface is 1:(1.2~1.8).

[0034] Optionally, the ratio of the hydroxyl groups of the organosilicon resin matrix with aryl functional structure to the hydroxyl groups of the boron-containing compound on the surface is 1:(1.3~1.7).

[0035] Optionally, the ratio of the hydroxyl groups of the organosilicon resin matrix with aryl functional structure to the hydroxyl groups of the boron-containing compound on the surface is 1:1.5.

[0036] Optionally, the hydroxyl content of the organosilicon resin matrix with an aryl functional structure on the surface is 0.05~2 mol%. Since the hydroxyl content affects the amount of boron introduced, if the hydroxyl content is too low, the boron content will be insufficient, resulting in poor damping effect; if the hydroxyl content is too high, it will also lead to a poorer reinforcing effect of the resin reinforcing additive, resulting in a deterioration in the mechanical properties of the final prepared composite rubber material product.

[0037] Optionally, the boron-containing compound is selected from one or more of boric acid, phenylboronic acid, tetrahydroxydiboronic acid, 1,4-phenyldiboronic acid, 1,3-phenyldiboronic acid, biphenyldiboronic acid, and anthracene-9,10-diboronic acid.

[0038] Optionally, the preparation steps include one or two of the following conditions: i) The reaction temperature between the silicone resin matrix with an aryl functional structure on the surface and the boron-containing compound is 90~150℃; ii) The reaction time between the organosilicon resin matrix with an aryl functional structure and the boron-containing compound is 6~24h.

[0039] Optionally, the boiling point of the organic solvent is not lower than the reaction temperature.

[0040] Optionally, the organic solvent is one or both of toluene and xylene.

[0041] Optionally, the surface of the silicone resin matrix containing an aryl functional structure is pre-dehydrated.

[0042] Optionally, the dehydration treatment includes one or two of the following conditions: i) Vacuum dry at 50~80℃ for 6~24h; ii) Organic solvents are dehydrated by molecular sieves for 12-48 hours.

[0043] Optionally, the boron-containing compound is pre-dissolved in an alcohol solvent before being added to the reaction system.

[0044] Optionally, the boron-containing compound is ultrasonically dispersed for 10-60 min before being added to the reaction system.

[0045] Optionally, the heating reaction is carried out using a staged heating method.

[0046] Optionally, the staged heating includes: first reacting at 60~90℃ for 1~4h; then heating to 100~150℃ for 4~12h.

[0047] Optionally, the obtained boron-containing resin-type wide-temperature-range damping additive may be further subjected to thermal curing treatment.

[0048] Optionally, the heat curing treatment conditions are: treatment under vacuum at 60~100℃ for 2~12 hours.

[0049] This application provides the use of the above-mentioned boron-containing resin-type wide-temperature-range damping additive as a damping additive for silicone rubber.

[0050] Optionally, the silicone rubber is one or more of methyl silicone rubber, methyl vinyl silicone rubber, phenyl silicone rubber, fluorosilicone rubber, and nitrile silicone rubber. It should be noted that the silicone rubbers listed above are common types, and the application scope of this application is not limited to the types listed above. Those skilled in the art can adjust the type of silicone rubber as needed.

[0051] This application provides a silicone rubber damping material, which includes silicone rubber and the above-mentioned boron-containing resin-type wide-temperature-range damping additive.

[0052] Optionally, the amount of the boron-containing resin-type wide-temperature-range damping additive is 1~50wt%. It should be noted that those skilled in the art can adjust the amount as needed.

[0053] Optionally, the silicone rubber is one or more of methyl silicone rubber, methyl vinyl silicone rubber, phenyl silicone rubber, fluorosilicone rubber, and nitrile silicone rubber.

[0054] This application provides a method for preparing the above-mentioned silicone rubber damping material, comprising the following steps: Add raw silicone rubber to a kneader, add silica and mix evenly to obtain silicone rubber compound; Take the silicone rubber compound on a two-roll mill, add the vulcanizing agent and boron-containing resin-type wide-temperature-range damping additive, and mix evenly. After vulcanization, a silicone rubber damping material is obtained.

[0055] This application provides the application of the aforementioned silicone rubber damping material in aerospace, weaponry, marine vehicles, or electromechanical systems.

[0056] The beneficial effects of this application include, but are not limited to: 1. Based on the boron-containing resin-type wide-temperature-range damping additive, its preparation method, and its application, a dynamic boron-oxygen structure is introduced for the first time on the surface of an organosilicon resin with a three-dimensional network structure. This overcomes the problem of the single dissipation mechanism in the prior art, thereby constructing a resin-type dynamic dissipation structure that is different from the flexible linear polysiloxane system. It realizes the synergistic effect of multiple energy dissipation mechanisms, such as dynamic boron-oxygen bond dissipation and π-π interaction between aryl groups. While maintaining the stability and mechanical properties of the resin network, it improves the high-temperature damping performance of the material and broadens the effective damping temperature range.

[0057] 2. The boron-containing resin-type wide-temperature-range damping additive, its preparation method, and its application provided in this application have good compatibility with silicone rubber, do not undergo phase separation with silicone rubber, and can provide good damping performance for silicone rubber, greatly expanding the effective damping temperature range of silicone rubber, which is a significant improvement compared with the prior art.

[0058] 3. According to the boron-containing resin-type wide-temperature-range damping additive of this application, its preparation method and application, the effective damping temperature range is increased by 152℃, the temperature range of tanδ>0.2 is increased by 71℃, and it does not affect the glass transition temperature of silicone rubber. It has excellent mechanical properties, with a maximum tensile strength of 6.3MPa, good fatigue resistance and long service life. Therefore, it can greatly broaden the application range of damping silicone rubber.

[0059] 4. Based on the boron-containing resin-type wide-temperature-range damping additive, its preparation method, and its application, the damping additive provided in this application can be used to prepare silicone rubber damping materials with silicone rubber as the matrix. These materials have excellent damping performance, a wide damping temperature range, and good mechanical properties, which can meet the market demand for high-performance damping silicone rubber.

[0060] 5. The boron-containing resin-type wide-temperature-range damping additive of this application, its preparation method and application, has a simple preparation process, low preparation cost and is easy to commercialize. Attached Figure Description

[0061] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings: Figure 1 This is a schematic diagram of the structure of the boron-containing resin-type wide-temperature-range damping additive involved in this application; Figure 2 The infrared spectra of the boron-containing resin-type wide-temperature-range damping additives involved in Examples 1-4 and Comparative Example 1 of this application are shown (the left image is the overall Fourier transform infrared spectrum, and the right image is a partial enlarged image). Figure 3This is a graph showing the elemental content of the boron-containing resin-type wide-temperature-range damping additives involved in Examples 1-4 of this application, as determined by XPS. Figure 4 To add a comparison graph of the dynamic mechanical (DMA) curves of the phenyl silicone rubber damping composite materials of Examples 1-4 and Comparative Examples 1-2 of this application; Figure 5 These are scanning electron microscope (SEM) images of the prepared products involved in Examples 1-4 of this application. Detailed Implementation

[0062] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments. Unless otherwise specified, the raw materials and reagents in the embodiments of the present application are all purchased through commercial channels.

[0063] like Figure 1 The diagram shows a schematic representation of the boron-containing resin-type wide-temperature-range damping additive involved in the application. Exemplary examples of boron-containing and aryl-containing functional structures are provided in the diagram. It should be noted that the proposed solution is not limited to this. Figure 1 The type of the example in the text.

[0064] The present application solution will be described below through specific embodiments.

[0065] Example 1 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) Mix 20g (0.005mol) of diphenyl MQ resin (hydroxyl content 0.1mol%) with 100ml of xylene in a 250ml three-necked flask equipped with a reflux condenser. Place the flask in an oil bath with a magnetic stirrer and slowly add 1.55g (0.025mol) of boric acid while stirring at room temperature. Stir at room temperature for 30min, then heat to 120℃ and stir at 120℃ for 10h.

[0066] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted boric acid, then remove the xylene solvent by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin type wide temperature range damping additive product.

[0067] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 4231.

[0068] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with a phenyl molar content of 30%), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 1, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0069] Example 2 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) Mix 20g (0.005mol) of diphenyl MQ resin (hydroxyl content 0.1mol%) with 100ml of xylene in a 250ml three-necked flask equipped with a reflux condenser. Place the flask in an oil bath with a magnetic stirrer and slowly add 3.66g (0.03mol) of phenylboronic acid while stirring at room temperature. Stir at room temperature for 30min, then raise the temperature to 120℃ and stir at 120℃ for 10h.

[0070] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted phenylboronic acid, then remove the solvent xylene by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin type wide temperature range damping additive product.

[0071] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 4353.

[0072] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with a phenyl molar content of 30%), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 2, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0073] Example 3 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) Mix 20g (0.005mol) of diphenyl MQ resin (hydroxyl content 0.1mol%) with 100ml of xylene in a 250ml three-necked flask equipped with a reflux condenser. Place the flask in an oil bath with a magnetic stirrer and slowly add 1.22g (0.02mol) of tetrahydroxydiboron while stirring at room temperature. Stir at room temperature for 30min, then raise the temperature to 120℃ and stir at 120℃ for 10h.

[0074] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted tetrahydroxydiboron, then remove the solvent xylene by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin type wide temperature range damping additive product.

[0075] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 4332.

[0076] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with 30% phenyl molar content), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 3, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0077] Example 4 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) Mix 20g (0.005mol) of diphenyl MQ resin (hydroxyl content 0.1mol%) with 100ml of xylene in a 250ml three-necked flask equipped with a reflux condenser. Place the flask in an oil bath with a magnetic stirrer and slowly add 3.32g (0.02mol) of 1,4-phenylenediboric acid while stirring at room temperature. Stir at room temperature for 30min, then raise the temperature to 120℃ and stir at 120℃ for 10h.

[0078] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted 1,4-benzenediboric acid, then remove the xylene solvent by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin-type wide temperature range damping additive product.

[0079] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 4514.

[0080] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with a phenyl molar content of 30%), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 4, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0081] Comparative Example 1 The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with 30% phenyl molar content), 50 parts by weight of silica TS530, 30 parts by weight of diphenyl MQ resin-type damping additive, and 2 parts by weight of vulcanizing agent bis2,4. First, the phenyl silicone rubber raw rubber was placed in a kneader, and silica TS530 was added in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and diphenyl MQ resin-type damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at 100°C for 10 minutes and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0082] Comparative Example 2 The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (30% phenyl molar content monophenyl silicone rubber), 50 parts by weight of silica TS530, without any damping additives, and 2 parts by weight of vulcanizing agent bis2,4. First, the phenyl silicone rubber raw rubber was placed in a kneader, and silica TS530 was added in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 was added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at 100°C for 10 minutes and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0083] like Figure 2 The image shows the infrared spectra of the boron-containing resin-type wide-temperature-range damping additives involved in Examples 1-4 and Comparative Example 1 (the left image is the overall Fourier transform infrared spectrum, and the right image is a partial magnified view). The spectra show the peak temperature at 1370 cm⁻¹. -1 A bending vibration absorption peak of Si-OB can be observed at [value missing] cm⁻¹, and the appearance of this characteristic peak indicates the successful synthesis of boron-containing MQ resin. Furthermore, in the range of 10⁵⁰–10¹⁰ cm⁻¹... -1 Si appears at the location O-bond stretching vibration absorption peak, 791 cm⁻¹ -1 and 2956 cm -1 The absorption peaks at these locations are the stretching vibrations of -Si(CH3)2 and -CH3, respectively, from 3070 to 3000 cm⁻¹. -1 The absorption peak obtained at this point is attributed to the stretching vibration of the CH bond on the benzene ring.

[0084] like Figure 3 The figure shown is an XPS-measured elemental composition diagram of the boron-containing resin-type wide-temperature-range damping additives involved in Examples 1-4, which can further verify the success of boron modification.

[0085] like Figure 4 The figure shown is a comparison of the dynamic mechanical (DMA) curves of the phenyl silicone rubber damping composite materials of Examples 1-4 and Comparative Examples 1-2.

[0086] like Figure 5 The image shown is a scanning electron microscope image of the products prepared in Examples 1-4. The morphology characterization results show that the surface height difference of the four composite materials is small, indicating that the boron-containing MQ resin and the phenyl silicone rubber matrix have good compatibility. All four boron-containing MQ resins can be uniformly dispersed in the phenyl silicone rubber matrix, and the two have good compatibility and will not undergo phase separation.

[0087] In addition, the mechanical and dynamic mechanical properties of the damping silicone rubber material were tested, and the results are shown in Tables 1 and 2.

[0088] Table 1 Mechanical properties of damping silicone rubber materials

[0089] Table 2 Damping properties of damping silicone rubber materials

[0090] The difference between the damping additives prepared in Examples 1-4 and Comparative Example 1 is that the damping additives in the examples contain boron, which can form boron-oxygen dynamic bonds in the phenyl silicone rubber composite material.

[0091] Comparative Example 1 shows that the damping performance of phenyl silicone rubber composites can only be improved by increasing intermolecular friction through the steric hindrance effect of the phenyl group. However, due to its singular energy dissipation mechanism, the improvement in damping performance is relatively small. In contrast, boron-containing resin-type wide-temperature-range damping additives not only contain phenyl groups with a large steric hindrance effect but also boron-oxygen dynamic bonds. Under stress, these boron-oxygen dynamic bonds can dissipate energy through reversible breakage and recombination, significantly improving the damping performance of the composite material.

[0092] Compared to phenyl silicone rubber without the damping additive of this invention, silicone rubber with the added damping additive exhibits significantly improved temperature ranges (tanδ > 0.3 and tanδ > 0.2) and a significantly improved loss factor at 150°C, while also possessing excellent mechanical properties. This is because the boron-containing resin-type wide-temperature-range damping additive can form boron-oxygen dynamic bonds with phenyl silicone rubber. The introduction of these dynamic bonds leads to dissociation and association under dynamic strain in the damping composite material, thereby increasing energy loss and significantly improving the damping performance of the phenyl silicone rubber. This results in a wider effective damping temperature range and superior mechanical properties.

[0093] Researchers found that the differences in mechanical properties are related to the structure and boron content of the boron-containing MQ resin. Composite materials modified with boron-containing MQ resin with high boron content also have the highest content of dynamic bonds, resulting in the highest mechanical properties. This shows that boron-oxygen dynamic bonds have an effect on improving mechanical strength.

[0094] Researchers also found that boron-containing MQ resin not only improved the energy dissipation capacity of phenyl silicone rubber, but also enhanced its ability to absorb impact energy. Dynamic mechanical analysis and cyclic tensile tests jointly demonstrated that the improvement of damping performance by boron-containing MQ resin is related to its boron content. The higher the boron content, the more boron-oxygen dynamic bonds are generated in the composite material system, and the better the damping performance.

[0095] In addition, the introduction of boron can significantly improve the heat resistance of composite materials. It can increase the overall bond energy of the system by forming boron-oxygen dynamic bonds. At the same time, the bond energy of boron-oxygen covalent bonds is high, much higher than that of carbon-carbon bonds, so materials with higher boron content have better heat resistance.

[0096] Example 5 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) Mix 20g (0.002mol) of diphenyl MQ resin with a number average molecular weight of about 10,000 (hydroxyl content 0.5mol%) with 100ml of xylene in a 250ml three-necked flask equipped with a reflux condenser. Place the flask in an oil bath with a magnetic stirrer and slowly add 3.32g (0.02mol) of 1,4-phenylenediboric acid while stirring at room temperature. Stir at room temperature for 30min, then raise the temperature to 120℃ and stir at 120℃ for 10h.

[0097] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted 1,4-benzenediboric acid, then remove the xylene solvent by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin-type wide temperature range damping additive product.

[0098] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 10523.

[0099] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with 30% phenyl molar content), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 5, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0100] Example 6 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) Mix 20g (0.02mol) of monophenyl MDT resin with a number average molecular weight of about 1000 (hydroxyl content 0.1mol%) with 100ml of xylene in a 250ml three-necked flask equipped with a reflux condenser. Place the flask in an oil bath with a magnetic stirrer and slowly add 3.32g (0.02mol) of 1,4-phenylenediboric acid while stirring at room temperature. Stir at room temperature for 30min, then raise the temperature to 120℃ and stir at 120℃ for 10h.

[0101] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted 1,4-benzenediboric acid, then remove the xylene solvent by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin-type wide temperature range damping additive product.

[0102] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 1204.

[0103] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with a phenyl molar content of 30%), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 6, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0104] Example 7 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) Mix 20g (0.005mol) of diphenyl MT resin (hydroxyl content 1mol%) with a number average molecular weight of about 4000 with 100ml of xylene in a 250ml three-necked flask equipped with a reflux condenser. Place the flask in an oil bath with a magnetic stirrer and slowly add 3.32g (0.02mol) of 1,4-phenylenediboric acid while stirring at room temperature. Stir at room temperature for 30min, then raise the temperature to 120℃ and stir at 120℃ for 10h.

[0105] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted 1,4-benzenediboric acid, then remove the xylene solvent by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin-type wide temperature range damping additive product.

[0106] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 4427.

[0107] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with a phenyl molar content of 30%), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 7, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0108] Example 8 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) Mix 20g (0.005mol) of diphenylMTQ resin (hydroxyl content 2.0mol%) with 100ml of xylene in a 250ml three-necked flask equipped with a reflux condenser. Place the flask in an oil bath with a magnetic stirrer and slowly add 3.32g (0.02mol) of 1,4-phenylenediboric acid while stirring at room temperature. Stir at room temperature for 30min, then raise the temperature to 120℃ and stir at 120℃ for 10h.

[0109] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted 1,4-benzenediboric acid, then remove the xylene solvent by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin-type wide temperature range damping additive product.

[0110] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 4458.

[0111] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with a phenyl molar content of 30%), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 8, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0112] Example 9 A method for preparing a boron-containing resin-based wide-temperature-range damping additive includes the following steps: (1) 20g (0.005mol) of phenyl POSS silicone resin with a number average molecular weight of about 4000 (due to the incomplete condensation of phenyl POSS silicone resin, a small amount of hydroxyl groups are present on its surface. In this example, the hydroxyl content of the raw material is 0.05mol%) and 100ml of xylene are mixed in a 250ml three-necked flask equipped with a reflux condenser. The flask is placed in an oil bath with a magnetic stirrer. 3.32g (0.02mol) of 1,4-phenylenediboric acid is slowly added under the condition of stirring at room temperature. The mixture is stirred at room temperature for 30min, and then heated to 120℃ and stirred at 120℃ for 10h.

[0113] (2) Cool the crude product containing xylene solvent to room temperature, filter to remove unreacted 1,4-benzenediboric acid, then remove the xylene solvent by rotary evaporation, and then dry it in a vacuum oven at 70°C for 24 hours to obtain a boron-containing resin-type wide temperature range damping additive product.

[0114] The number average molecular weight of this boron-containing resin-type wide-temperature-range damping additive is 4310.

[0115] The raw materials were weighed according to the following ratio: 100 parts by weight of phenyl silicone rubber raw rubber (monophenyl silicone rubber with a phenyl molar content of 30%), 50 parts by weight of silica TS530, 30 parts by weight of the damping additive from Example 9, and 2 parts by weight of vulcanizing agent bis2,4. The phenyl silicone rubber raw rubber was first placed in a kneader, and silica TS530 was added to it in several batches. After mixing evenly at 50°C, the rubber compound was removed and allowed to stand at room temperature for 16 hours. Then, 2 parts by weight of vulcanizing agent bis2,4 and the above-mentioned boron-containing resin-type wide-temperature-range damping additive were added to a two-roll mill and mixed evenly at 30°C. A first-stage vulcanization was then performed using a vacuum vulcanizing machine at a vulcanization temperature of 100°C, a vulcanization time of 10 minutes, and a vulcanization pressure of 10 MPa. Finally, a second-stage vulcanization was performed using a forced-air oven at 180°C for 4 hours to obtain a 2 mm thick rubber sheet for testing.

[0116] Experiments and tests revealed that the products prepared in Examples 5-9 exhibited the same excellent performance as those in Example 4, especially with a significantly wider effective damping temperature range, without affecting the glass transition temperature of silicone rubber, excellent mechanical properties, good fatigue resistance, and long service life.

[0117] Example 10 The process is basically the same as in Example 4, except that the diphenyl MQ resin is placed in a vacuum drying oven and dried at 60°C for 12 hours to remove trace amounts of moisture; and 100 ml of xylene is pre-dehydrated with a 4 Å molecular sieve for 24 hours to ensure that the solvent is free of water and impurities.

[0118] Example 11 The reaction was basically the same as in Example 4, except that 1,4-phenylenediboric acid was pre-dissolved in 10 ml of anhydrous ethanol, sonicated for 30 min to promote dissolution, and then the 1,4-phenylenediboric acid-ethanol solution was added dropwise to the reaction system.

[0119] Example 12 The process is basically the same as in Example 4, except that after stirring at room temperature for 30 minutes, the temperature is first raised to 80°C and reacted for 2 hours to allow boric acid and MQ resin to undergo initial condensation. Then, the temperature is raised to 120°C at a rate of 5°C / min and stirred at 120°C for 8 hours.

[0120] Example 13 The product is basically the same as Example 4, except that after drying in a vacuum oven at 70°C for 24 hours, it also includes a step of vacuum heat curing at 85°C for 6 hours to obtain a boron-containing resin-type wide-temperature-range damping additive product.

[0121] The researchers conducted performance tests on the products prepared in Examples 10-13, and the results are shown in Tables 3 and 4 below.

[0122] Table 3 Mechanical properties of damping silicone rubber materials

[0123] Table 4 Damping properties of damping silicone rubber materials

[0124] By comparing the data with that of Example 4, it can be seen that: In Example 10, pre-dehydration treatment of the diphenyl MQ resin and organic solvent effectively reduced free water in the system, suppressed the self-condensation reaction between boron-containing compounds, and made the Si-OB dynamic structure more uniformly distributed on the resin network surface. Compared with Example 4, the loss factor of the damping material obtained in Example 10 at 150°C increased from 0.31 to 0.35, and the effective damping temperature range of tanδ>0.3 increased from 175°C to 183°C, indicating that moderately reducing the water content of the system is beneficial to improving the degree of dynamic structure formation and high-temperature dissipation capability.

[0125] In Example 11, by pre-dissolving and ultrasonically dispersing 1,4-phenylenediboric acid, the dispersion uniformity of boron-containing compounds in the system can be improved, reducing local enrichment of boron structures and local cross-linking phenomena, resulting in a more uniform distribution of dynamic boron-oxygen structures. Compared with Example 4, the peak tanδ of the damping material obtained in Example 11 increased from 0.57 to 0.64, the effective damping temperature range of tanδ > 0.2 increased from 330℃ to 340℃, and the tensile strength of the material increased from 5.6 MPa to 5.9 MPa, indicating that uniform dispersion is beneficial to the formation of interfacial dissipation and the synergistic effect of dynamic dissipation structures.

[0126] In Example 12, a staged heating method was adopted. Initial condensation of the boron-containing structure with the resin surface was achieved at a lower temperature, followed by a further increase in temperature to promote the stable formation of the Si-OB structure. This effectively reduced the localized gelation problem caused by rapid high-temperature polymerization. Compared to Example 4, the tanδ curve plateau region of the damping material obtained in Example 12 was significantly broadened, indicating that staged condensation is beneficial for constructing a more stable and uniform resin-type dynamic dissipative structure.

[0127] In Example 13, subsequent vacuum thermal curing treatment promotes further condensation of residual active groups, improves the dynamic structural stability of Si-OB, and reduces small molecule residues in the system. Compared to Example 4, the loss factor of the damping material obtained in Example 13 at 150°C increased from 0.31 to 0.36, indicating that thermal curing treatment is beneficial to improving the long-term stability and heat resistance of the resin-type dynamic dissipative structure.

[0128] The above description is merely an embodiment of this application, and the scope of protection of this application is not limited to these specific embodiments, but is determined by the claims 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 technical concept and principles of this application should be included within the scope of protection of this application.

Claims

1. A boron-containing resin-based wide-temperature-range damping additive, characterized in that, The boron-containing resin-type wide-temperature-range damping additive comprises: A) An organosilicon resin matrix with a three-dimensional network structure; B) A boron-containing functional structure connected to the silicone resin matrix; C) An aryl-containing functional structure connected to the organosilicon resin matrix; The boron-containing functional structure is connected to the surface of the three-dimensional network structure of the organosilicon resin matrix via Si-OB bonds; the aryl-containing functional structure is located on the surface of the three-dimensional network structure of the organosilicon resin matrix. The molecular weight of the organosilicon resin matrix is ​​1000~10000.

2. The boron-containing resin-type wide-temperature-range damping additive according to claim 1, characterized in that, The silicone resin matrix is ​​selected from one or more of MQ resin, MT resin, MTQ resin, MDT resin, and POSS silicone resin.

3. The preparation method of the boron-containing resin-type wide-temperature-range damping additive as described in claim 1 or 2, characterized in that, Includes the following steps: Mix an organosilicon resin matrix with an aryl functional structure on its surface with an organic solvent; Add a boron-containing compound and mix thoroughly; The heating reaction yields a crude product of a boron-containing resin-type wide-temperature-range damping additive. After purification, a boron-containing resin-type wide-temperature-range damping additive was obtained.

4. The preparation method of the boron-containing resin-type wide-temperature-range damping additive according to claim 3, characterized in that, The ratio of the hydroxyl groups of the organosilicon resin matrix with aryl functional structure to the hydroxyl groups of the boron-containing compound is 1:(0.5~2).

5. The preparation method of the boron-containing resin-type wide-temperature-range damping additive according to claim 3, characterized in that, The boron-containing compound is selected from one or more of boric acid, phenylboronic acid, tetrahydroxydiboronic acid, 1,4-phenyldiboronic acid, 1,3-phenyldiboronic acid, biphenyldiboronic acid, and anthracene-9,10-diboronic acid.

6. The preparation method of the boron-containing resin-type wide-temperature-range damping additive according to claim 3, characterized in that, The preparation steps include one or two of the following conditions: i) The reaction temperature between the silicone resin matrix with an aryl functional structure on the surface and the boron-containing compound is 90~150℃; ii) The reaction time between the organosilicon resin matrix with an aryl functional structure and the boron-containing compound is 6~24h.

7. The use of the boron-containing resin-type wide-temperature-range damping additive as described in claim 1 or 2 as a damping additive for silicone rubber.

8. A silicone rubber damping material, characterized in that, The silicone rubber damping material includes silicone rubber and the boron-containing resin-type wide-temperature-range damping additive as described in claim 1 or 2.

9. The method for preparing the silicone rubber damping material as described in claim 8, characterized in that, Includes the following steps: Add raw silicone rubber to a kneader, add silica and mix evenly to obtain silicone rubber compound; Take the silicone rubber compound on a two-roll mill, add the vulcanizing agent and boron-containing resin-type wide-temperature-range damping additive, and mix evenly. After vulcanization, a silicone rubber damping material is obtained.

10. The application of the silicone rubber damping material as described in claim 8 in aerospace, weaponry, marine vehicles, or electromechanical applications.

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