High-temperature-resistant resin, composite material and preparation method and application thereof

Abstract

The invention provides high-temperature-resistant resin, a composite material and a preparation method and application thereof, and relates to the technical field of high polymer materials. According to the high-temperature-resistant resin, organic silicon resin with good flexibility and heat resistance is organically combined with phenolic resin with a high carbon residue rate and a ceramic precursor with high-temperature ceramization capability through molecular design, molecular-level hybrid crosslinking is achieved, a unique three-dimensional network structure is formed, the synergistic high-temperature-resistant effect is achieved, and the high-temperature-resistant resin is prepared. The comprehensive performance is improved by adding the nano reinforcing filler, the composite curing agent, the interface modifier and the like, so that the obtained high-temperature-resistant resin has excellent high-temperature resistance, can resist high temperature of 400 DEG C or above for a long time, can resist high temperature of 600 DEG C for a short time, has excellent mechanical properties, overcomes the defect of high brittleness of the traditional high-temperature-resistant resin, and is suitable for industrial production. And the high-temperature-resistant resin also has good forming process performance. The invention also provides a preparation method of the high-temperature-resistant resin and a composite material prepared from the high-temperature-resistant resin.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a high-temperature resistant resin, a composite material, its preparation method, and its application. Background Technology

[0002] High-temperature resistant resins have wide applications in aerospace, new energy, and electronics industries. Traditional high-temperature resistant resins such as epoxy resin, phenolic resin, and silicone resin each have their own advantages and disadvantages: epoxy resin has good mechanical properties but limited temperature resistance (generally <300℃); phenolic resin has good heat resistance but is brittle; silicone resin has excellent temperature resistance but insufficient mechanical strength.

[0003] In recent years, progress has been made in resin modification research. Organosilicon-modified epoxy resins, through chemical grafting or physical blending, achieve molecular-level synergy, increasing toughness by over 40% and breaking through the 300℃ thermal decomposition temperature. Hyperbranched polysiloxane (HPS)-modified epoxy resin systems combine good heat resistance (glass transition temperature >190°C) and toughness (elongation at break >3%). Boron-modified phenolic resins achieve a 70% carbon residue at 900℃ and a decomposition peak temperature as high as 625℃.

[0004] However, existing modified resins still struggle to meet the requirements for long-term use above 400℃. While silicone resins possess excellent thermal stability, their mechanical strength is insufficient; phenolic resins have high carbon residue but poor toughness; ceramic precursor resins exhibit excellent temperature resistance but are difficult to process. A single resin system cannot simultaneously satisfy the requirements for high-temperature performance, mechanical strength, and processability.

[0005] In view of this, the present invention is hereby proposed. Summary of the Invention

[0006] The present invention aims to provide a high-temperature resistant resin, a composite material, a preparation method thereof, and its application, so as to improve the above-mentioned problems existing in the prior art.

[0007] To achieve the above objectives, the following technical solution is adopted: The primary objective of this invention is to provide a high-temperature resistant resin, comprising the following raw materials in parts by weight: The composition includes 40-60 parts of silicone resin, 20-40 parts of phenolic resin, 10-30 parts of ceramic precursor, 5-25 parts of nano-reinforcing filler, 3-15 parts of composite curing agent, and 1-8 parts of interface modifier; among which... The total weight of the organosilicon resin, phenolic resin and ceramic precursor is 100 parts.

[0008] Furthermore, based on the above-mentioned technical solution of the present invention, the organosilicon resin includes organosilicon resins containing phenyl and / or vinyl groups. And / or, the phenolic resin includes allylated phenolic resin and / or boron-modified phenolic resin; And / or, the ceramic precursor comprises polycarbosilane and / or polysilazane; And / or, the nano-reinforcing filler includes at least two of carbon nanotubes, graphene, nano-alumina, hollow glass microspheres, boron nitride, nano-zirconia, or calcined kaolin, preferably including carbon nanotubes, graphene, and nano-alumina. And / or, the composite curing agent includes a platinum catalyst, an amine curing agent, and a free radical initiator; And / or, the interface modifier includes silane coupling agents and / or titanate coupling agents.

[0009] Furthermore, based on the above-mentioned technical solution of the present invention, the thermal decomposition temperature Td5% of the high-temperature resin is >450℃, and the residual carbon rate at 800℃ under a nitrogen atmosphere is >70%; And / or, the high-temperature resistant resin has a flexural strength ≥420MPa and an elongation at break ≥2.8%.

[0010] The second objective of this invention is to provide a method for preparing the above-mentioned high-temperature resistant resin, comprising the following steps: (a) Dissolve the silicone resin in a solvent, add the nano-reinforcing filler, mix evenly, and obtain the modified silicone resin; (b) Phenolic resin is heated to a molten state, ceramic precursor is added, and the reaction is carried out under an inert atmosphere to form phenolic-ceramic prepolymer; (c) The modified silicone resin, phenolic-ceramic prepolymer and interface modifier are mixed and reacted to obtain an intermediate product; (d) Remove the solvent from the intermediate product, add the composite curing agent, mix evenly and then cure to obtain a high-temperature resistant resin.

[0011] Furthermore, based on the above technical solution of the present invention, in step (a), the solvent includes at least one of xylene, toluene or tetrahydrofuran; And / or, in step (b), the temperature at which the phenolic resin reacts with the ceramic precursor is 120-150°C and the reaction time is 0.5-2 hours; And / or, in step (c), the reaction temperature is 120-140°C and the reaction time is 2-4 hours.

[0012] The third objective of this invention is to provide a composite material prepared using the above-mentioned high-temperature resistant resin and reinforcing material.

[0013] Furthermore, based on the above-described technical solution of the present invention, the reinforcing material includes fibers; and / or, the interlaminar shear strength of the composite material is ≥35MPa.

[0014] The fourth objective of this invention is to provide a method for preparing the above-mentioned composite material, comprising the following steps: The reinforcing material is impregnated with the high-temperature resistant resin and then subjected to curing and post-curing treatments to obtain a composite material. The curing process includes a medium-temperature curing stage and a high-temperature curing stage.

[0015] Furthermore, based on the above technical solution of the present invention, the curing temperature of the medium-temperature curing stage is 120-150℃, and the curing time is 2-4 hours. And / or, the curing temperature of the high-temperature curing stage is 200-250℃, and the curing time is 2-3 hours; And / or, the post-curing treatment is performed at a temperature of 300-350°C for 1-2 hours.

[0016] The fifth objective of this invention is to provide the application of the above-mentioned high-temperature resistant resin or composite material in the fields of aerospace, new energy or electronics industry.

[0017] Compared with the prior art, the technical solution of the present invention has at least the following technical effects: (1) This invention provides a high-temperature resistant resin. Through molecular design, an organosilicon resin with good flexibility and heat resistance is organically combined with a phenolic resin with high carbon residue and a ceramic precursor with high-temperature ceramicization capability. This allows for molecular-level hybrid crosslinking to form a unique three-dimensional network structure, achieving a synergistic high-temperature resistance effect. Furthermore, by adding nano-reinforcing fillers, composite curing agents, interface modifiers, etc., the comprehensive performance is improved. The obtained high-temperature resistant resin has excellent high-temperature resistance, can withstand temperatures above 400℃ for a long time, and can withstand temperatures up to 600℃ for a short time. It also has excellent mechanical properties, overcoming the problem of high brittleness of traditional high-temperature resistant resins. Moreover, this high-temperature resistant resin also has good molding process performance, such as low low-temperature viscosity (viscosity at 40℃ is only about 500 mPa·s), long pot life (>6h), and low curing temperature (≤350℃). It is suitable for various processes such as RTM, filament winding, pultrusion, and molding.

[0018] (2) The present invention also provides a method for preparing a high-temperature resistant resin. The preparation method adopts a stepwise reaction and gradient construction strategy, which effectively avoids problems such as excessively fast gelation and phase separation that may be caused by direct mixing of multiple components, and ensures the uniformity and high performance of the final product.

[0019] (3) The present invention also provides a composite material prepared using the high-temperature resistant resin and reinforcing material provided by the present invention. Given that the high-temperature resistant resin can simultaneously meet the requirements of high-temperature performance, mechanical strength and processability, it can be used to prepare various high-performance composite materials, and the high-performance composite materials prepared have broad application prospects in aerospace, new energy, electronics industry and other fields. Attached Figure Description

[0020] Figure 1 The above is a DSC test chart of the high-temperature resistant resin obtained in Example 1 of this invention. Figure 2 This is a TGA test image of the high-temperature resistant resin prepared in Example 1 of the present invention under air conditions; Figure 3 This is a schematic diagram of the curing process of the high-temperature resistant resin provided by the present invention. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Those skilled in the art should understand that the embodiments described are merely illustrative of the invention and should not be considered as specific limitations thereof. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. Process parameters not specifically specified in the following embodiments are generally performed under conventional conditions.

[0022] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0023] According to a first aspect of the present invention, a high-temperature resistant resin is provided, comprising, by weight, the following raw materials: 40-60 parts of silicone resin, 20-40 parts of phenolic resin, 10-30 parts of ceramic precursor, 5-25 parts of nano-reinforced filler, 3-15 parts of composite curing agent and 1-8 parts of interface modifier. The total weight of the organosilicon resin, phenolic resin and ceramic precursor is 100 parts.

[0024] This invention uses silicone resin, phenolic resin, and ceramic precursor as the resin matrix. The silicone resin primarily provides flexibility and heat resistance, and its dosage is also limited. Excessive silicone resin dosage (e.g., above 60 parts) can lead to excessive flexibility and insufficient rigidity, significantly reducing the modulus and high-temperature dimensional stability of the high-temperature resistant resin, and substantially increasing costs. Insufficient silicone resin dosage (e.g., below 40 parts) may be insufficient to effectively encapsulate and toughen the brittle network of the phenolic resin, resulting in poor overall toughness, easy cracking, and decreased thermal shock resistance of the high-temperature resistant resin. Therefore, typical but non-limiting parts by weight of silicone resin are 40, 42, 45, 48, 50, 52, 55, 58, or 60 parts, or any range between any two points.

[0025] Phenolic resin is mainly used to provide high carbon residue and ablation resistance. The amount of phenolic resin used has a certain impact on the performance of high-temperature resistant resins. If the amount of phenolic resin is too high (e.g., above 40 parts), it generally causes a sharp increase in the brittleness of the system, a significant decrease in the elongation at break, and the generation of internal stress during processing, leading to cracking. It also reduces the compatibility with silicone resins. If the amount of phenolic resin is too low (e.g., below 20 parts), it cannot provide a sufficiently high carbon residue skeleton, resulting in a carbon residue of less than 65% at 800℃ and insufficient retention of mechanical properties at high temperatures. Therefore, typical but non-limiting parts by weight of phenolic resin are 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, etc., and any range between any two points.

[0026] Ceramic precursors are primarily used to provide high-temperature ceramization capabilities, and their dosage needs to be controlled within a suitable range. If the dosage of ceramic precursor is too high (e.g., above 30 parts), a large number of small-molecule byproducts will be generated during the curing and post-curing stages, easily leading to increased internal porosity, a significant decrease in mechanical properties (especially flexural strength), and potentially causing defects such as blistering and cracking. If the dosage of ceramic precursor is too low (e.g., below 10 parts), a continuous and effective ceramic network cannot be formed at high temperatures, resulting in limited contribution to improving the carbon residue rate and oxidation resistance of high-temperature resistant resins at 800℃, failing to achieve the effect of "ceramization reinforcement." Therefore, typical but non-limiting weight parts of ceramic precursors are 10, 12, 15, 18, 20, 25, or 30 parts, or any range between these values.

[0027] Nano-reinforcing fillers can improve the mechanical strength of high-temperature resistant resins, but the amount of nano-reinforcing fillers used should not be too high or too low. If the amount of nano-reinforcing fillers is too high (e.g., higher than 25 parts), they are prone to agglomeration and are difficult to disperse evenly, thus becoming stress concentration points, reducing the resin's fracture toughness and strength, and significantly increasing the resin viscosity, thus deteriorating processability. If the amount of nano-reinforcing fillers is too low (e.g., lower than 5 parts), the reinforcing effect is not obvious and cannot effectively improve mechanical strength. Therefore, typical but non-limiting weight parts of nano-reinforcing fillers are 5, 6, 8, 10, 12, 15, 18, 20, 22, or 25 parts, as well as any range between any two points.

[0028] Composite curing agents are primarily used to accelerate resin curing and improve product performance. Typical, but not limiting, weight percentages of composite curing agents are 3, 5, 6, 8, 10, or 15 parts, or any range between any two points. These composite curing agents are essential in high-temperature resistant resins. Under conventional process conditions, without using composite curing agents to control reactivity, the resin system cannot simultaneously meet the requirements of low viscosity, long pot life, and controllable gel behavior for RTM (Regenerative Thermal Mold) and molding. However, under specific temperature programs or component autocatalytic design, molding can also be achieved through intrinsic reactions.

[0029] Interface modifiers are mainly used to build chemical bridges between the organic phase (resin matrix) and the inorganic phase (nano-reinforcing filler), thereby improving the bonding strength between various materials. Typical, but not limiting, weight parts of interface modifiers are 1 part, 2 parts, 3 parts, 5 parts, or 8 parts, as well as any range between any two points.

[0030] The high-temperature resistant resin of this invention utilizes molecular design, nanocomposite technology, and hybrid crosslinking to organically combine a silicone resin with good flexibility and heat resistance, a phenolic resin with high carbon residue, and a ceramic precursor with high-temperature ceramicization capability. Furthermore, the addition of nano-reinforcing fillers enhances the overall performance. The resulting high-temperature resistant resin exhibits excellent high-temperature resistance, capable of withstanding temperatures above 400°C for extended periods and up to 600°C for short periods. It also possesses excellent mechanical properties, overcoming the brittleness problem of traditional high-temperature resistant resins. Moreover, it exhibits good molding processability, such as low low-temperature viscosity (viscosity at 40°C is only about 500 mPa·s), long pot life (>6h), and low curing temperature (≤350°C), making it suitable for various processes including RTM, filament winding, pultrusion, and compression molding.

[0031] As an optional embodiment of the technical solution of the present invention, the silicone resin is selected from silicone resins containing phenyl and / or vinyl groups, such as silicone resins containing only phenyl groups, or silicone resins containing only vinyl groups, or preferably silicone resins containing both phenyl and vinyl groups.

[0032] When organosilicon resins contain phenyl groups, the large phenyl group (benzene ring) can increase the rigidity of the molecular chain and raise the glass transition temperature (Tg) of the organosilicon resin. g It improves thermal stability and compatibility with aromatic phenolic resins.

[0033] When organosilicon resin contains vinyl groups, the vinyl groups, as active functional groups, can undergo hydrosilylation reactions with the Si-H bonds in the ceramic precursor under the action of a platinum catalyst, thereby achieving chemical bonding between the organosilicon resin and the ceramic precursor, rather than simple physical blending, which is beneficial for forming a stable hybrid network structure.

[0034] Organosilicon resins containing only phenyl groups include, but are not limited to, phenylmethyl silicone resins. For example, the brand name of phenylmethyl silicone resin may be: POWERSIL® Resin 700, purchased from Wacker Chemie.

[0035] Organosilicon resins containing only vinyl groups include, but are not limited to, vinyl methyl silicone resins. For example, the brand name of vinyl methyl silicone resin may be SK-VR-8290, purchased from Shenzhen Tianqi New Materials.

[0036] Organosilicon resins containing both phenyl and vinyl groups include, but are not limited to, phenyl vinyl silicone resins. For example, the grade of phenyl vinyl silicone resin may be AM304, purchased from Guangzhou Xinhou Chemical.

[0037] As an optional embodiment of the technical solution of the present invention, the phenolic resin is selected from allylated phenolic resin and / or boron-modified phenolic resin.

[0038] The allyl group (-CH2-CH=CH2) in allylated phenolic resin has high reactivity and can crosslink with organosilicon resin or other components under the action of free radical initiators to form a denser network structure.

[0039] The introduction of boron (B) into boron-modified phenolic resin can form BOC or BC bonds, significantly increasing the resin's thermal decomposition temperature and carbon residue (carbon residue can reach over 70% at 800℃), and improving its antioxidant properties.

[0040] Both allylated phenolic resin and boron-modified phenolic resin are commercially available products. For example, allylated phenolic resin can be purchased from Beijing Jinjiete New Material Technology Co., Ltd., and boron-modified phenolic resin can be purchased from Jining Tangyi Chemical Co., Ltd.

[0041] As an optional embodiment of the technical solution of the present invention, the ceramic precursor includes polycarbosilane and / or polysilazane. Polycarbosilane and polysilazane are also commercially available products; for example, polycarbosilane (PCS) can be purchased from Ningbo Zhongxing New Material Technology Co., Ltd.; polysilazane (PSN) can be purchased from Zhonggui New Material (Quanzhou) Co., Ltd.

[0042] As an optional embodiment of the technical solution of the present invention, the nano-reinforcing filler includes at least one of carbon nanotubes, graphene or nano-alumina, preferably including but not limited to carbon nanotubes, graphene and nano-alumina.

[0043] In the preparation of high-temperature resistant resins, the nano-reinforcing fillers are mixed and modified with organosilicon resins, forming a core-shell structure within the resin: carbon nanotubes / graphene as the core and nano-alumina as the shell. Through multi-scale reinforcement using a composite system of carbon nanotubes, graphene, and nano-alumina, the mechanical properties of the high-temperature resistant resins can be significantly improved.

[0044] As a preferred embodiment of the technical solution of the present invention, while maintaining the ternary composite system of carbon nanotubes, graphene and nano alumina, the nano-reinforcing filler further includes, but is not limited to, hollow glass microspheres, ceramic microspheres or boron nitride and other auxiliary fillers. The total amount of auxiliary fillers shall not exceed 10 parts, so as to synergistically improve the thermal insulation of high temperature resistant resin or reduce the material density, but should not replace the main reinforcing phase.

[0045] As an optional embodiment of the technical solution of the present invention, the composite curing agent includes a platinum catalyst, an amine curing agent, and a free radical initiator.

[0046] As a preferred embodiment of the technical solution of the present invention, the amine curing agent includes at least one of 4,4'-diaminodiphenyl sulfone (DDS), dicyandiamide (DICY), m-phenylenediamine (m-PDA) or diaminodiphenylmethane (DDM); Preferably, the free radical initiator includes at least one of dicumyl peroxide (DCP), 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (TMCH), tert-butyl peroxide (TBPB), or 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DBPH).

[0047] A composite system consisting of a platinum catalyst, an amine curing agent, and a free radical initiator works synergistically to achieve a dual or even triple curing mechanism. The amine curing agent ensures initial molding at medium temperatures (~150℃); the free radical initiator and platinum catalyst are activated at high temperatures (≥200℃) to complete the final dense crosslinking and hybrid network construction. Single or binary curing systems cannot simultaneously achieve optimal pot life, curing speed, and final network density.

[0048] As an optional embodiment of the technical solution of the present invention, the interface modifier includes a silane coupling agent (e.g., KH550) and / or a titanate coupling agent, preferably including a silane coupling agent and a titanate coupling agent.

[0049] Chemical bonds are formed by the reaction of silane coupling agents with the Si-OH groups of organosilicon resins.

[0050] By using a combination of silane coupling agents and titanate coupling agents, the interfacial compatibility and bonding strength between the resin matrix and nano-reinforcing fillers (such as carbon nanotubes, graphene, and nano-alumina) as well as between the resin matrix and inorganic fibers (such as carbon fibers and glass fibers) in subsequent composite materials can be further improved.

[0051] The high-temperature resistant resin obtained by this invention has good heat resistance and mechanical properties.

[0052] As an optional embodiment of the technical solution of the present invention, the thermal decomposition temperature of the high-temperature resistant resin is >450℃, preferably ≥500℃, for example 500℃, 510℃, 515℃, 517℃, 520℃, 522℃, 525℃ or 535℃, etc.; the residual carbon rate of the high-temperature resistant resin at 800℃ under nitrogen atmosphere is >70%, for example 71%, 72%, 73%, 75%, 76%, 78% or 79%, etc.

[0053] As an optional embodiment of the technical solution of the present invention, the flexural strength of the high-temperature resistant resin is ≥420MPa, for example, 430MPa, 435MPa, 440MPa, 450MPa or 465MPa, and the elongation at break is ≥2.8%, for example, 2.8%, 3.2%, 3.5%, 3.8%, 4.0% or 4.5%.

[0054] The high-temperature resistant resin prepared by this invention has the characteristics of low viscosity at low temperature (viscosity is only about 500 mPa·s at 40℃), long pot life (>6h), and low curing temperature (≤350℃). It is suitable for various molding processes such as winding, RTM, pultrusion, and compression molding in the subsequent preparation of fiber composite materials.

[0055] According to a second aspect of the present invention, a method for preparing the high-temperature resistant resin provided in the first aspect of the present invention is provided, comprising the following steps: (a) Dissolve the silicone resin in a solvent, add the nano-reinforcing filler, mix to disperse evenly, and obtain the modified silicone resin; (b) Phenolic resin is heated to a molten state, ceramic precursor is added, and the reaction is carried out under an inert atmosphere to form phenolic-ceramic prepolymer; (c) The modified silicone resin, phenolic-ceramic prepolymer and interface modifier are mixed and reacted to obtain an intermediate product; (d) Remove the solvent from the intermediate product, add the composite curing agent, mix evenly, and obtain a high-temperature resistant resin.

[0056] In step (a) of this invention, because the organosilicon resin has a relatively low viscosity and contains polar groups, it is beneficial to uniformly and stably disperse the nano-reinforcing filler through ultrasonic and mechanical stirring, forming a modified organosilicon resin reinforced with the nano-reinforcing filler. If the nano-reinforcing filler is added in subsequent steps, it is prone to agglomeration due to the high viscosity of the system, thus failing to exert its reinforcing effect. Therefore, in step (a), the modification of the organosilicon resin is achieved by adding the nano-reinforcing filler.

[0057] In step (b), the phenolic hydroxyl groups (-OH) of the molten phenolic resin can undergo dehydrogenation coupling or transesterification reactions with the active Si-H, Si-CH3, or Si-NH groups in the ceramic precursor (polycarbosilane (PCS) or polysilazane) under a high-temperature inert atmosphere to form preliminary Ph-O-Si chemical bonds, thus forming a phenolic-ceramic prepolymer.

[0058] In step (c), a molecular-level hybrid crosslinking reaction occurs between the modified silicone resin, the phenolic-ceramic prepolymer, and the interface modifier.

[0059] In step (d), a composite curing agent is added to obtain a high-temperature resistant resin.

[0060] This invention provides a method for preparing a high-temperature resistant resin. The method adopts a stepwise reaction and gradient construction strategy, which effectively avoids problems such as excessively rapid gelation and phase separation that may be caused by direct mixing of multiple components, and ensures the uniformity and high performance of the final product.

[0061] As an optional embodiment of the technical solution of the present invention, in step (a), the solvent includes at least one of xylene, toluene or tetrahydrofuran (THF).

[0062] As an optional implementation of the technical solution of the present invention, in step (a), uniform dispersion is achieved by ultrasonic dispersion and mechanical stirring.

[0063] As an optional embodiment of the technical solution of the present invention, in step (b), the inert atmosphere includes at least one of nitrogen or argon; And / or, in step (b), the temperature at which the phenolic resin reacts with the ceramic precursor is 120-150°C (e.g., 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or 150°C, etc.), and the reaction time is 0.5-2 hours (e.g., 0.5 hours, 1 hour, 1.5 hours, or 2 hours, etc.).

[0064] As an optional implementation of the technical solution of the present invention, in step (c), the reaction temperature is 120-140℃ (e.g., 120℃, 125℃, 130℃, 135℃ or 140℃, etc.), and the reaction time is 2-4 hours (e.g., 2 hours, 3 hours or 4 hours, etc.).

[0065] By further limiting the reaction temperature and reaction time in step (c), the vinyl / phenyl active groups in the modified organosilicon resin can fully undergo hydrosilylation and / or condensation reactions with the Si–H, phenolic hydroxyl and other functional groups in the phenolic-ceramic prepolymer, thereby constructing a uniform, dense and highly cross-linked organic-inorganic hybrid network structure at the molecular scale.

[0066] According to a third aspect of the present invention, a composite material is provided, which is prepared using the high-temperature resistant resin and reinforcing material provided in the first aspect of the present invention.

[0067] The high-temperature resistant resin provided by this invention can be combined with reinforcing materials to prepare various high-performance composite materials, thus having broad application prospects in aerospace, new energy, electronics industry and other fields.

[0068] As an optional embodiment of the technical solution of the present invention, the reinforcing material includes fibers, preferably inorganic fibers, such as carbon fibers, glass fibers or quartz fibers.

[0069] The high-temperature resistant resin provided by this invention has excellent compatibility with inorganic fibers and can form a strong interface with carbon fiber, glass fiber, quartz fiber, etc. The interlaminar shear strength of the composite material is ≥35MPa.

[0070] According to a fourth aspect of the present invention, a method for preparing a composite material is provided, comprising the following steps: impregnating a reinforcing material with a high-temperature resistant resin provided in the first aspect of the present invention, followed by curing and post-curing treatment to obtain the composite material.

[0071] The high-temperature resistant resin provided by this invention has low viscosity at low temperatures (viscosity at 40℃ is only about 500 mPa·s), long pot life (>6h), and low curing temperature (≤350℃), making it suitable for various molding processes such as winding, RTM, pultrusion, and compression molding, thus overcoming the limitation of poor processability of high-temperature resins.

[0072] As an optional embodiment of the technical solution of the present invention, the curing process adopts a dual curing mechanism, specifically including a medium-temperature curing stage and a high-temperature curing stage; wherein... The curing temperature of the medium-temperature curing stage is 120-150℃ (e.g., 120℃, 125℃, 130℃, 135℃, 140℃, 145℃ or 150℃, etc.), and the curing time is 2-4 hours (e.g., 2 hours, 3 hours or 4 hours, etc.). The resin can be initially cross-linked through amine curing agents in this medium-temperature curing stage. The curing temperature of the high-temperature curing stage is 200-250℃ (e.g., 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃ or 250℃, etc.), and the curing time is 2-3 hours (e.g., 2 hours, 3 hours or 4 hours, etc.). This high-temperature curing stage can achieve deep cross-linking through free radical initiators and platinum catalysts.

[0073] By employing a dual curing mechanism and a composite curing agent system, it achieves the characteristics of low-temperature curing and high-temperature use, balancing processability and temperature resistance.

[0074] As an optional embodiment of the technical solution of this invention, the post-curing treatment temperature is 300-350℃ (e.g., 300℃, 305℃, 310℃, 315℃, 320℃, 325℃, 330℃, 335℃, 340℃, 345℃, or 350℃, etc.), and the time is 1-2 hours (e.g., 1 hour, 1.5 hours, or 2 hours, etc.). The post-curing treatment can initially ceramize the ceramic precursor, forming a three-dimensional network structure.

[0075] In addition, with Figure 3 Using the schematic diagram of the curing process of the high-temperature resistant resin of this invention as an example, the curing process of the high-temperature resistant resin of this invention will be briefly described. Stage 1 is a liquid prepolymer after mixing the resin (organosilicon resin, phenolic resin and ceramic precursor) with a composite curing agent. Its viscosity at 40°C is low, only about 500 mPa·s, and it has a long pot life (>6h) suitable for fiber impregnation. Stage 2 corresponds to the medium-temperature curing stage (e.g., 120-150°C / 2-4h), in which an amine curing agent constructs a primary cross-linking network. Stage 3 covers high-temperature curing (e.g., 200-250°C / 2-3h) and post-curing treatment (e.g., 300-350°C / 1-2h), in which deep cross-linking and ceramization are completed through the reaction of free radical initiators and platinum catalysts, ultimately forming an "organic-inorganic hybrid" high-temperature resistant network structure.

[0076] The fifth aspect of the present invention provides the application of the high-temperature resistant resin provided in the first aspect of the present invention or the composite material provided in the third aspect of the present invention in the fields of aerospace, new energy or electronics industry.

[0077] Given the advantages of the high-temperature resistant resin or composite material made from it provided by this invention, it has good application prospects in the fields of aerospace, new energy or electronics industry.

[0078] The present invention will be further described in detail below with reference to specific embodiments and comparative examples. Among the raw materials used in the following embodiments and comparative examples: the carbon nanotubes are multi-walled carbon nanotubes with a diameter of 10-30 nm, a length of 5-20 μm, and a purity ≥95 wt%; the graphene is few-layer graphene with a sheet diameter of 0.5-5 μm, 1-5 layers, and a carbon content ≥95 wt%; the nano-alumina has a primary particle size of 20-80 nm, is spherical, and has a purity ≥99.5 wt%; the silane coupling agent KH-550 was purchased from Nanjing Nengde Chemical Co., Ltd., brand name ND-550; the titanate coupling agent was purchased from Nanjing Nengde Chemical Co., Ltd., brand name NDZ-201.

[0079] Example 1 This embodiment provides a high-temperature resistant resin, which, by weight, comprises the following raw materials: Silicone resin: 50 parts, phenyl vinyl silicone resin (brand name: POWERSIL® Resin 700, Wacker Chemie); Phenolic resin: 30 parts, allylated phenolic resin (with an allyl substitution degree of 0.4-0.7 mol / per phenol unit, a softening point of 75-90°C, and a free phenol content of less than 2.0 wt%, purchased from Beijing Jinjiete New Material Technology Co., Ltd.); Ceramic precursor: 20 parts, polycarbosilane (liquid polycarbosilane with a number-average molecular weight (Mn), viscosity at 25°C of 500-2000 mPa·s, and Si / C atomic ratio of 1.0-1.2, purchased from Ningbo Zhongxing New Material Technology Co., Ltd.); Solvent: Xylene, 30 parts; Composite curing agent: 1 part platinum catalyst (xylene solution of Karstedt type platinum catalyst, platinum content 2.0 wt%), 2 parts dicyandiamide and 2 parts dicumyl peroxide; Nano-reinforced filler: consists of 5 parts carbon nanotubes and 3 parts graphene; Interface modifier: includes 2 parts silane coupling agent KH-550 and 1 part titanate coupling agent.

[0080] The preparation method of the high-temperature resistant resin in this embodiment includes the following steps: (a) Dissolve the formulated amount of organosilicon resin in xylene, where the weight of xylene is 60% of the weight of organosilicon resin. Add the formulated amount of nano-reinforcing filler and ultrasonically disperse for 2 hours to achieve uniform dispersion, thereby obtaining modified organosilicon resin. (b) Heat the phenolic resin of the formula amount to 120°C to make it melt, add the ceramic precursor of the formula amount, and react at 130°C for 1 hour under nitrogen protection to form phenolic-ceramic prepolymer; (c) The modified silicone resin and phenolic-ceramic prepolymer were mixed, and the interface modifier of the specified amount was added. The mixture was reacted at 130°C for 3 hours to obtain the intermediate product. (d) Remove the solvent from the intermediate product by vacuum distillation, add the formulated amount of composite curing agent, stir and mix evenly to obtain high temperature resistant resin.

[0081] Example 2 This embodiment provides a high-temperature resistant resin. Except that the weight parts of the silicone resin used in Example 1 are adjusted from 50 parts to 60 parts, and the weight parts of the phenolic resin are adjusted from 30 parts to 20 parts, while the total weight parts of the silicone resin, phenolic resin and ceramic precursor remain at 100 parts, the types and amounts of other raw materials and the preparation method of the high-temperature resistant resin are the same as in Example 1.

[0082] Example 3 This embodiment provides a high-temperature resistant resin. Except that the weight parts of the silicone resin used in Example 1 are adjusted from 50 parts to 40 parts, and the weight parts of the phenolic resin are adjusted from 30 parts to 40 parts, while the total weight parts of the silicone resin, phenolic resin and ceramic precursor remain at 100 parts, the types and amounts of other raw materials and the preparation method of the high-temperature resistant resin are the same as in Example 1.

[0083] Example 4 This embodiment provides a high-temperature resistant resin. Except that the weight parts of the silicone resin used in Example 1 are adjusted from 50 parts to 56.25 parts, the weight parts of the phenolic resin are adjusted from 30 parts to 33.75 parts, and the weight parts of the ceramic precursor are adjusted from 20 parts to 10 parts, while the total weight parts of the silicone resin, phenolic resin, and ceramic precursor remain at 100 parts, the types and amounts of other raw materials and the preparation method of the high-temperature resistant resin are the same as in Example 1.

[0084] Example 5 This embodiment provides a high-temperature resistant resin. Except that the weight parts of the silicone resin used in Example 1 are adjusted from 50 parts to 43.75 parts, the weight parts of the phenolic resin are adjusted from 30 parts to 26.25 parts, and the weight parts of the ceramic precursor are adjusted from 20 parts to 30 parts, while the sum of the weight parts of the silicone resin, phenolic resin, and ceramic precursor remains 100 parts, the types and amounts of other raw materials and the preparation method of the high-temperature resistant resin are the same as in Example 1.

[0085] Example 6 This embodiment provides a high-temperature resistant resin. Except that the nano-reinforced filler used in Example 1 is adjusted to include 3 parts carbon nanotubes, 3 parts graphene and 2 parts nano alumina, the other raw material types, amounts and preparation methods of the high-temperature resistant resin are the same as in Example 1.

[0086] Example 7 This embodiment provides a high-temperature resistant resin, which, by weight, comprises the following raw materials: Organosilicon resin: 55 parts, phenyl vinyl silicone resin (brand name: POWERSIL® Resin 700, Wacker Chemie); Phenolic resin: 25 parts, boron-modified phenolic resin (with boron content of 0.8-3.5 wt%, phenolic hydroxyl content of 3.0-5.5 mmol / g, weight-average molecular weight of 900-2200 g / mol and molecular weight distribution (PDI) ≤ 2.0, purchased from Beijing Jinjiete New Material Technology Co., Ltd.); Ceramic precursor: 20 parts, polysilazane (PSN, with Si-H content of 0.7-2.5 wt%, weight-average molecular weight of 600-1800 g / mol, viscosity at 25℃ of 50-500 mPa·s, purchased from Zhonggui New Materials (Quanzhou) Co., Ltd.); Solvent: Xylene, 33 parts; Composite curing agent: 1 part platinum catalyst (xylene solution of Karstedt type platinum catalyst, platinum content 2.0 wt%), 2 parts dicyandiamide and 2 parts dicumyl peroxide; Nano-reinforced filler: 2 parts carbon nanotubes, 4 parts graphene and 6 parts nano alumina; Interface modifier: includes 2 parts silane coupling agent KH-550 and 1 part titanate coupling agent.

[0087] The preparation method of the high-temperature resistant resin in this embodiment includes the following steps: (a) Dissolve the formulated amount of organosilicon resin in xylene, where the weight of xylene is 60% of the weight of organosilicon resin. Add the formulated amount of nano-reinforcing filler and ultrasonically disperse for 2 hours to achieve uniform dispersion, thereby obtaining modified organosilicon resin. (b) Heat the phenolic resin of the formula amount to 120°C to make it melt, add the ceramic precursor of the formula amount, and react at 140°C for 1 hour under nitrogen protection to form phenolic-ceramic prepolymer; (c) The modified silicone resin and phenolic-ceramic prepolymer were mixed, and the formulated amount of interface modifier was added. The mixture was reacted at 140°C for 2 hours to obtain the intermediate product. (d) Remove the solvent from the intermediate product by vacuum distillation, add the formulated amount of composite curing agent, mix evenly, and obtain high temperature resistant resin.

[0088] Example 8 This embodiment provides a composite material comprising the following parts by weight of raw materials: 100 parts of the high-temperature resistant resin provided in Example 1 and 60 parts of the reinforcing material T700S carbon fiber (Toray Industries, Japan).

[0089] The method for preparing the composite material in this embodiment includes the following steps: High-temperature resistant resin is injected into the mold cavity using the RTM process to impregnate T700S carbon fiber. Then, curing and post-curing treatments are performed in a closed mold. The curing process includes a medium-temperature curing stage and a high-temperature curing stage. The medium-temperature curing stage is 130℃ / 2h, and the high-temperature curing stage is 250℃ / 2h. Post-curing treatment: 300℃ / 1h + 350℃ / 1h; The demolding temperature is ≤60℃, and the resulting material is a carbon fiber composite material.

[0090] Example 9 This embodiment provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Example 2, and the other raw material types and amounts are the same as in Example 1.

[0091] Example 10 This embodiment provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Example 3, and the other raw material types and amounts are the same as in Example 1.

[0092] Example 11 This embodiment provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Example 4, and the other raw material types and amounts are the same as in Example 1.

[0093] Example 12 This embodiment provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Example 5, and the other raw material types and amounts are the same as in Example 1.

[0094] Example 13 This embodiment provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Example 6, and the other raw material types and amounts are the same as in Example 1.

[0095] Example 14 This embodiment provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Example 7, and the other raw material types and amounts are the same as in Example 1.

[0096] Comparative Example 1 This comparative example provides a high-temperature resistant resin. Except that no phenolic resin was added to the raw materials of Example 1, the weight of the organosilicon resin was adjusted from 50 parts to 80 parts, and the types and amounts of the other raw materials were the same as in Example 1.

[0097] The preparation method of this comparative high-temperature resistant resin is the same as that of Example 1, except that steps (b) and (c) are not performed, and the modified organosilicon resin and ceramic prepolymer are not directly mixed.

[0098] Comparative Example 2 This comparative example provides a high-temperature resistant resin. Except that phenolic resin was not added to the raw materials of Example 1, the weight parts of the silicone resin were adjusted from 50 parts to 71.5 parts, and the weight parts of the ceramic precursor were adjusted from 20 parts to 28.5 parts, so that the sum of the weight parts of the silicone resin and the ceramic precursor was 100 parts. The weight ratio of silicone resin to ceramic precursor was kept the same as in Example 1, and the types and amounts of the other raw materials were the same as in Example 1.

[0099] The preparation method of this comparative high-temperature resistant resin is the same as that of Example 1, except that steps (b) and (c) are not performed, and the modified organosilicon resin and ceramic prepolymer are not directly mixed.

[0100] Comparative Example 3 This comparative example provides a high-temperature resistant resin. Except that no silicone resin was added to the raw materials of Example 1, the weight parts of phenolic resin were adjusted from 30 parts to 60 parts, and the weight parts of ceramic precursor were adjusted from 20 parts to 40 parts, so that the sum of the weight parts of phenolic resin and ceramic precursor was 100 parts, and the weight ratio of phenolic resin to ceramic precursor was kept the same as in Example 1. The amount and type of other raw materials were the same as in Example 1.

[0101] The preparation method of this comparative high-temperature resistant resin includes the following steps: (a) Heat the phenolic resin of the formula amount to 120°C to make it melt, add the ceramic precursor of the formula amount, and react at 130°C for 1 hour under nitrogen protection to form phenolic-ceramic prepolymer; (b) Dissolve the phenolic-ceramic prepolymer in 30 parts of xylene solvent, add the formulated amount of nano-reinforcing filler, and ultrasonically disperse for 2 hours to achieve uniform dispersion, thereby obtaining a phenolic-ceramic prepolymer-reinforcing filler solution. (c) Add the formulated amount of interface modifier to the phenolic-ceramic prepolymer-reinforced filler solution and react at 130°C for 3 hours to obtain the intermediate product; (d) Remove the solvent from the intermediate product by vacuum distillation, add the formulated amount of composite curing agent, mix evenly, and obtain high temperature resistant resin.

[0102] Comparative Example 4 This comparative example provides a high-temperature resistant resin. Except that no ceramic precursor was added to the raw materials of Example 1, the weight parts of the silicone resin were adjusted from 50 parts to 62.5 parts, and the weight parts of the phenolic resin were adjusted from 30 parts to 37.5 parts, so that the sum of the weight parts of the silicone resin and the phenolic resin was 100 parts. The weight ratio of the silicone resin and the phenolic resin was kept the same as in Example 1. The types and amounts of the other raw materials were the same as in Example 1.

[0103] The preparation method of this comparative high-temperature resistant resin is the same as that of Example 1, except that step (b) and step (c) are not performed and the modified silicone resin and phenolic resin are not directly mixed.

[0104] Comparative Example 5 This comparative example provides a high-temperature resistant resin. Except that the weight parts of the organosilicon resin in the raw materials of Example 1 are adjusted from 50 parts to 75 parts, the weight parts of the phenolic resin are adjusted from 30 parts to 18 parts, and the weight parts of the ceramic precursor are adjusted from 20 parts to 7 parts, the types, amounts, and preparation methods of the other raw materials are the same as in Example 1.

[0105] Comparative Example 6 This comparative example provides a high-temperature resistant resin. Except that the weight parts of the organosilicon resin in the raw materials of Example 1 are adjusted from 50 parts to 60 parts, the weight parts of the phenolic resin are adjusted from 30 parts to 35 parts, and the weight parts of the ceramic precursor are adjusted from 20 parts to 5 parts, the types, amounts, and preparation methods of the other raw materials are the same as in Example 1.

[0106] Comparative Example 7 This comparative example provides a high-temperature resistant resin. Except that the weight parts of the organosilicon resin in the raw materials of Example 1 are adjusted from 50 parts to 60 parts, the weight parts of the phenolic resin are adjusted from 30 parts to 10 parts, and the weight parts of the ceramic precursor are adjusted from 20 parts to 30 parts, the types, amounts, and preparation methods of the other raw materials are the same as in Example 1.

[0107] Comparative Example 8 This comparative example provides a high-temperature resistant resin. Except that the weight parts of the organosilicon resin in the raw materials of Example 1 are adjusted from 50 parts to 30 parts, the weight parts of the phenolic resin are adjusted from 30 parts to 40 parts, and the weight parts of the ceramic precursor are adjusted from 20 parts to 30 parts, the types, amounts, and preparation methods of the other raw materials are the same as in Example 1.

[0108] Comparative Example 9 This comparative example provides a high-temperature resistant resin, except that no nano-reinforcing filler was added to the raw materials of Example 1, while the types and amounts of other raw materials are the same as those in Example 1.

[0109] The preparation method of this comparative high-temperature resistant resin is the same as that of Example 1, except that no nano-reinforcing filler is added in step (a).

[0110] Comparative Example 10 This comparative example provides a high-temperature resistant resin. Except for changing the specific type of organosilicon resin in the raw materials of Example 1 from phenyl vinyl silicone resin to Grade A MQ resin (DY-MQ803, Shandong Dayi Chemical Co., Ltd.), the other raw material types, amounts, and preparation methods of the high-temperature resistant resin are the same as in Example 1.

[0111] Comparative Example 11 This comparative example provides a high-temperature resistant resin. Except that the specific type of phenolic resin in the raw materials of Example 1 is changed from allylated phenolic resin to general-purpose phenolic resin (PF-207, Shandong Chenghui New Material Co., Ltd.), that is, non-allylated phenolic resin and non-boron modified phenolic resin, the other types of raw materials, dosages, and preparation methods of the high-temperature resistant resin are the same as in Example 1.

[0112] Comparative Example 12 This comparative example provides a high-temperature resistant resin. Except that the composite curing agent dicyandiamide was not added to the raw materials in Example 1, the types and amounts of the other raw materials and the preparation method of the high-temperature resistant resin are the same as in Example 1.

[0113] Comparative Example 13 This comparative example provides a high-temperature resistant resin, the raw material composition of which is the same as that of Example 1.

[0114] The preparation method of this comparative high-temperature resistant resin mainly involves adjusting the feeding sequence of the nano-reinforced filler, specifically including the following steps: (a) Dissolve the prescribed amount of silicone resin in xylene, where the weight of xylene is 60% of the weight of silicone resin, and ultrasonically disperse for 2 hours to achieve uniform dispersion, thereby obtaining a silicone resin solution. (b) Heat the phenolic resin of the formula amount to 120°C to make it melt, add the ceramic precursor of the formula amount, and react at 130°C for 1 hour under nitrogen protection to form phenolic-ceramic prepolymer; (c) Mix the organosilicon resin solution and phenolic-ceramic prepolymer, add the formulated amount of interface modifier, and react at 130°C for 3 hours to obtain the intermediate product; (d) The solvent in the intermediate product is removed by vacuum distillation, and the formulated amount of nano-reinforcing filler and the formulated amount of composite curing agent are added and stirred to mix evenly to obtain high temperature resistant resin.

[0115] Comparative Example 14 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 1, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0116] Comparative Example 15 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin obtained in Comparative Example 2, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0117] Comparative Example 16 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 3, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0118] Comparative Example 17 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 4, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0119] Comparative Example 18 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 5, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0120] Comparative Example 19 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 6, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0121] Comparative Example 20 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 7, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0122] Comparative Example 21 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 8, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0123] Comparative Example 22 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 9, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0124] Comparative Example 23 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin obtained in Comparative Example 10, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0125] Comparative Example 24 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 11, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0126] Comparative Example 25 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin obtained in Comparative Example 12, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0127] Comparative Example 26 This comparative example provides a composite material, except that the high-temperature resistant resin in Example 8 is replaced with the high-temperature resistant resin prepared in Comparative Example 13, and the other raw material types, amounts, and preparation methods are the same as in Example 8.

[0128] Comparative Example 27 This comparative example provides a method for preparing a composite material. Except that the dual curing treatment in the preparation method of Example 8 is adjusted to only perform a high-temperature curing stage and not a medium-temperature curing stage, and the high-temperature curing stage is 250℃ / 2h, the raw material composition and process parameters of the composite material are the same as those in Example 8.

[0129] Comparative Example 28 This comparative example provides a method for preparing a composite material. Except for the absence of a post-curing treatment step in the preparation method of Example 8, the raw material composition and process parameters of the composite material are the same as those in Example 8.

[0130] To illustrate the technical effects of the various embodiments and comparative examples, the following experimental examples are provided.

[0131] Experimental Example 1 The properties of the high-temperature resistant resins and composite materials prepared in the various embodiments and comparative examples of the present invention were tested.

[0132] Among them, the glass transition temperature (T) g The glass transition step was measured by DSC (heating rate 10℃ / min, nitrogen atmosphere), and the fitted peak temperature was taken. Figure 1 The DSC curve obtained in Example 1 of this invention shows the curing exothermic peak and the glass transition temperature T. g T g It is approximately 211℃.

[0133] The thermal decomposition temperature is defined as the temperature corresponding to a 5% mass loss in the TGA test (Td5%), and the atmosphere is high-purity nitrogen. Figure 2 The TGA curve of the high-temperature resistant resin obtained in Example 1 of this invention shows that the thermal decomposition temperature Td5%≈522℃. Figure 2 The 38.8% corresponding to 800°C is the test data under air environment. The carbon residue rate at 800°C was measured to be 75% under nitrogen atmosphere, as shown in Table 1a.

[0134] In terms of mechanical properties, the flexural strength of high-temperature resistant resin and composite material was tested according to GB / T 9341-2008 and GB / T1449-2005, respectively; the interlaminar shear strength of composite material was tested according to GB / T 1450.1-2005; and the elongation at break was tested according to the test method of GB / T 1040.2-2022. The service life of the process performance is tested according to ASTM D2196-2020; the mechanical property retention rate is tested according to the heat aging test method (GB / T 7141-2008). The bending strength mechanical property is tested according to the aforementioned test standard, and the high temperature bending performance retention rate is calculated according to the formula: retention rate (%) = (bending strength after aging / original bending strength) × 100%.

[0135] For ease of explanation, the performance data are divided into two parts: Table 1a lists the thermal and mechanical properties of the high-temperature resistant resins prepared in each embodiment and comparative example; Table 1b lists the key performance indicators of the carbon fiber composite materials prepared from the above resins.

[0136] Table 1a High-temperature resistant resin performance data Table 1b Composite Material Performance Data Based on the data in Tables 1a and 1b, the following conclusions can be drawn: (1) The ternary hybrid resin system has an irreplaceable synergistic effect. The glass transition temperature Tg of Examples 1-7 gThe thermal decomposition temperature (Td5%) (202-220℃), thermal decomposition temperature (500-535℃), and flexural strength (425-465 MPa) are all significantly better than any of the two-component comparative examples (Comparative Examples 1-4). Among them, Comparative Example 3, due to the absence of silicone resin, has poor resin system compatibility, exhibits a high-viscosity paste at 40℃, with a viscosity significantly higher than that of the examples (>10,000 mPa·s), resulting in deteriorated processing performance. Furthermore, its cured product is highly brittle, with an elongation at break of only 1.5%. The data from Examples 1-7 and Comparative Examples 1-4 demonstrate that silicone resin provides a flexible network, phenolic resin contributes a rigid skeleton, and ceramic precursors promote high-temperature residual carbon. Together, these three components construct an integrated "rigid-flexible-ceramic" structure, overcoming the triangular contradiction of heat resistance, toughness, and processability.

[0137] (2) There is a strict window for the raw material ratio. When any component exceeds the limit of the present invention (such as comparative examples 5-8), the thermal stability or mechanical properties deteriorate significantly, indicating that controlling the mass ratio of organosilicon resin, phenolic resin and ceramic precursor to (40-60):(20-40):(10-30) is a necessary condition to achieve the best comprehensive performance.

[0138] (3) Specific types of resin are crucial. When using ordinary MQ silicone resin (Comparative Example 10) or general-purpose linear phenolic resin (Comparative Example 11), T g The decrease in both strength and properties by 5-10% confirms that the specific raw materials, such as methylphenyl silicone resin and allylated phenolic resin, as defined in this invention, play a decisive role in compatibility and reactivity.

[0139] (4) The composite curing agent system is indispensable. Comparative Example 12, due to the absence of the amine curing agent dicyandiamide, had a pot life shortened to 4.0 h and a Tg decrease of 13 °C, indicating that amine accelerators not only regulate the reaction rhythm but also participate in the construction of the primary crosslinking network, directly affecting the final performance.

[0140] (5) Nano-reinforced fillers need to be uniformly dispersed in situ. In Example 6, multi-scale synergistic reinforcement was achieved by introducing CNT / graphene / Al2O3 ternary fillers in situ, and the flexural strength reached 465 MPa; while in Comparative Example 13, the strength was only 330 MPa due to agglomeration caused by the addition of nano-fillers, highlighting the key influence of the preparation process on the nano-effect.

[0141] (6) The dual curing process ensures the integrity of the interface. The interlaminar shear strength of Comparative Example 27 (without medium-temperature curing) and Comparative Example 28 (without post-curing) decreased to 31.5 MPa and 36.0 MPa, respectively (38.5 MPa in Example 8), which proves that the gradient process of "medium-temperature curing to build the primary network + high-temperature post-curing to complete the deep cross-linking" is crucial for the fiber-resin interface bonding.

[0142] In summary, this invention successfully obtains a high-temperature resistant resin with high heat resistance, high mechanical strength, good processability, and excellent interfacial properties through specific resin combinations, precise proportions, special raw materials, composite curing systems, and optimized processes. This invention does not rely on high-temperature pyrolysis densification processes (only as a preferred option) nor pursues complete ceramization. Instead, it achieves a "ceramic-like precursor-reinforced organic-inorganic hybrid network" at a lower temperature, balancing processability, strength, and high-temperature stability. Primarily used as a resin matrix for high-performance composite materials, it is suitable for conventional polymer composite molding processes such as RTM, compression molding, and filament winding, and can be used to prepare high-temperature resistant structural / functional integrated components required in aerospace, new energy, and other fields.

[0143] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention shall be within the scope of protection of the pending claims of the present invention.

Claims

1. A high-temperature resistant resin, characterized in that, The ingredients include the following parts by weight: 40-60 parts of silicone resin, 20-40 parts of phenolic resin, 10-30 parts of ceramic precursor, 5-25 parts of nano-reinforced filler, 3-15 parts of composite curing agent and 1-8 parts of interface modifier. The total weight of the organosilicon resin, phenolic resin and ceramic precursor is 100 parts.

2. The high-temperature resistant resin according to claim 1, characterized in that, The silicone resin includes silicone resins containing phenyl and / or vinyl groups; And / or, the phenolic resin includes allylated phenolic resin and / or boron-modified phenolic resin; And / or, the ceramic precursor comprises polycarbosilane and / or polysilazane.

3. The high-temperature resistant resin according to claim 1, characterized in that, The nano-reinforced filler includes at least two of carbon nanotubes, graphene, nano-alumina, hollow glass microspheres, boron nitride, nano-zirconia, or calcined kaolin, preferably including carbon nanotubes, graphene, and nano-alumina. And / or, the composite curing agent comprises a platinum catalyst, an amine curing agent, and a free radical initiator; preferably, the amine curing agent comprises at least one of 4,4'-diaminodiphenyl sulfone, dicyandiamide, m-phenylenediamine, or diaminodiphenylmethane; preferably, the free radical initiator comprises at least one of dicumyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxide, or 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; And / or, the interface modifier includes silane coupling agents and / or titanate coupling agents.

4. The high-temperature resistant resin according to any one of claims 1-3, characterized in that, The thermal decomposition temperature (Td5%) of the high-temperature resistant resin is >450℃, and the residual carbon rate at 800℃ under nitrogen atmosphere is >70%. And / or, the high-temperature resistant resin has a flexural strength ≥420MPa and an elongation at break ≥2.8%.

5. The method for preparing the high-temperature resistant resin according to any one of claims 1-4, characterized in that, Includes the following steps: (a) Dissolve the silicone resin in a solvent, add the nano-reinforcing filler, mix evenly, and obtain the modified silicone resin; (b) Phenolic resin is heated to a molten state, ceramic precursor is added, and the reaction is carried out under an inert atmosphere to form phenolic-ceramic prepolymer; (c) The modified silicone resin, phenolic-ceramic prepolymer and interface modifier are mixed and reacted to obtain an intermediate product; (d) Remove the solvent from the intermediate product, add the composite curing agent, mix evenly, and obtain a high-temperature resistant resin.

6. The method for preparing the high-temperature resistant resin according to claim 5, characterized in that, In step (a), the solvent includes at least one of xylene, toluene, or tetrahydrofuran; And / or, in step (b), the temperature at which the phenolic resin reacts with the ceramic precursor is 120-150°C and the reaction time is 0.5-2 hours; And / or, in step (c), the reaction temperature is 120-140℃ and the reaction time is 2-4 hours.

7. A composite material, characterized in that, It is prepared using the high-temperature resistant resin and reinforcing material described in any one of claims 1-4; Preferably, the reinforcing material comprises fibers; Preferably, the interlaminar shear strength of the composite material is ≥35MPa.

8. The method for preparing the composite material according to claim 7, characterized in that, Includes the following steps: The reinforcing material is impregnated with the high-temperature resistant resin and then subjected to curing and post-curing treatments to obtain a composite material. The curing process includes a medium-temperature curing stage and a high-temperature curing stage.

9. The method for preparing the composite material according to claim 8, characterized in that, The curing temperature of the medium-temperature curing stage is 120-150℃, and the curing time is 2-4 hours. And / or, the curing temperature of the high-temperature curing stage is 200-250℃, and the curing time is 2-3 hours; And / or, the post-curing treatment is performed at a temperature of 300-350°C for 1-2 hours.

10. The application of the high-temperature resistant resin according to any one of claims 1-4 or the composite material according to claim 7 in the fields of aerospace, new energy or electronics industry.

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