Hybrid resin capable of generating gas by cracking in wide temperature range as well as preparation method and application of hybrid resin

Abstract

The invention relates to the technical field of high-performance heat-proof composite material matrix resin, in particular to hybrid resin capable of being cracked to produce gas in a wide temperature range as well as a preparation method and application of the hybrid resin. The hybrid resin composition comprises organic resin, an MAX phase component and / or an inorganic ceramic component, and the inorganic ceramic component is selected from an oxide ceramic component and / or a non-oxide ceramic component; wherein based on 100 parts by mass of the organic resin, the dosage of the MAX phase component is 0-100 parts by mass, the dosage of the inorganic ceramic component is 0-100 parts by mass, and the dosage of the MAX phase component and the dosage of the inorganic ceramic component are not 0 at the same time. The hybrid resin prepared from the hybrid resin composition has the advantages of cracking in a wide temperature range, high temperature resistance, oxidation resistance and self-enhancement; meanwhile, the preparation method simplifies the technological process and is convenient for large-scale industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of high-performance heat-resistant composite matrix resins, and particularly relates to a hybrid resin capable of pyrolyzing and generating gas in a wide temperature range, and a preparation method and application thereof. Background Art

[0002] With the development of modern aerospace technology, heat-resistant composite materials must face application challenges in extremely harsh thermal environments such as higher temperatures, longer durations, and oxidative environments. As a key component of heat-resistant composite materials, the pyrolysis behavior of high-performance matrix resins, such as pyrolysis temperature and range, pyrolysis gas composition and quantity, determines the mass ejection effect and air flow blockage effect of heat-resistant materials, thereby affecting the heat protection effect of the materials; at the same time, as the fiber protection component formed after high-temperature ablation, elements such as the composition, structure, morphology, and strength of the matrix resin directly affect the heat protection effect such as the ablation shaping performance of the materials.

[0003] Phenolic resin has a series of excellent properties such as high temperature resistance, high char yield, low smoke toxicity, low cost, self-extinguishing and flame retardancy, and is widely used in fields such as construction (thermal insulation materials), transportation (interior parts of large aircraft and high-speed trains), and metallurgy (refractory materials). At the same time, it is also the matrix resin of ablation heat-resistant composite materials that is most widely used and has the largest consumption in high-tech fields. However, from the perspective of pyrolysis behavior, the pyrolysis temperature range of traditional phenolic resin is between 300 - 900 °C. When the temperature is further increased, the phenolic resin basically no longer loses weight, which means that in the high-temperature stage above 900 °C, the mass ejection and air flow blockage effects of the phenolic resin matrix contribute very little to the heat protection effect of the material, and it is difficult to meet the requirement of further pyrolyzing and generating gas above 1000 °C to improve the heat protection effect. Moreover, due to the defects generated by the pyrolysis of organic components in the carbon layer formed by traditional phenolic resin, the strength and air flow shear resistance of the material are significantly reduced, and coupled with the poor antioxidant performance of this resin, it can no longer meet the heat protection requirements of materials in the new harsh thermal environment.

[0004] Silicone resin is another major type of matrix resin for ablative heat-resistant composite materials. Due to its molecular structure containing Si-O-Si structure, its antioxidant performance and high-temperature mass retention rate are improved compared with phenolic resin. However, the high-temperature resistance of the Si-O-Si main chain is relatively low. When the temperature exceeds 1200 °C, its skeleton structure softens and even undergoes structural collapse, and it can no longer meet the use requirements above 1500 °C.

[0005] In summary, traditional phenolic resin and silicone resin-based thermal protection composites cannot meet the new application requirements when facing challenges in harsh application environments such as higher temperatures, longer durations, and oxidation conditions. Due to problems such as insufficient temperature resistance grade of the matrix resin, narrow cracking temperature range, high porosity of the carbon-forming components, and low strength, it has become one of the core problems that must be solved in the development of matrix resins for the new generation of thermal protection materials. How to solve the long-term and continuous cracking gas generation of the matrix resin in a wide temperature range, strengthen the combined thermal protection effect of the mass ejection and gas flow blocking effects of the matrix resin, and improve the strength and erosion resistance of the fiber protection components formed after high-temperature ablation has become one of the core problems that must be solved in the development of matrix resins for the new generation of thermal protection materials. Summary of the Invention

[0006] The object of the present invention is to overcome the above technical problems and provide a hybrid resin composition capable of cracking and generating gas in a wide temperature range, a hybrid resin capable of cracking and generating gas in a wide temperature range, its preparation method and application. The hybrid resin prepared from the hybrid resin composition has the advantages of cracking in a wide temperature range, high temperature resistance, oxidation resistance, and self-strengthening. At the same time, the preparation method simplifies the process flow and is convenient for large-scale industrial production.

[0007] To achieve the above object, in the first aspect of the present invention, a hybrid resin composition capable of cracking and generating gas in a wide temperature range is provided. The hybrid resin composition includes: an organic resin, a MAX phase component, and / or an inorganic ceramic component, wherein the inorganic ceramic component is selected from an oxide ceramic component and / or a non-oxide ceramic component;

[0008] Among them, based on 100 parts by mass of the organic resin, the dosage of the MAX phase component is 0-100 parts by mass, the dosage of the inorganic ceramic component is 0-100 parts by mass, and the dosages of the MAX phase component and the inorganic ceramic component are not both 0 at the same time.

[0009] In the present invention, without special instructions, the hybrid resin composition including: an organic resin, a MAX phase component, and / or an inorganic ceramic component means that the hybrid resin composition includes: an organic resin and a MAX phase component; or, an organic resin and an inorganic ceramic component; or, an organic resin, a MAX phase component, and an inorganic ceramic component.

[0010] Preferably, the organic resin is selected from phenolic resin and / or silicone resin. The phenolic resin is selected from at least one of barium phenolic resin, amino phenolic resin, boron phenolic resin, sodium phenolic resin, boron-silicon hybrid phenolic resin, magnesium phenolic resin, and thermoplastic phenolic resin; the silicone resin is selected from at least one of methyl silicone resin, phenyl silicone resin, and vinyl phenyl silicone resin.

[0011] Preferably, the oxide ceramic component is selected from at least one of silicon oxide, boron oxide, aluminum oxide, zirconium oxide, and low melting point glass powder.

[0012] Preferably, the non-oxide ceramic component is selected from at least one of boron carbide, silicon carbide, zirconium carbide, hafnium carbide, tantalum carbide, zirconium diboride, titanium diboride, and elemental boron powder.

[0013] In a second aspect of the present invention, there is provided a hybrid resin capable of pyrolyzing and generating gas in a wide temperature range, which is prepared by subjecting the hybrid resin composition provided in the first aspect to a thermal polymerization reaction.

[0014] In a third aspect of the present invention, there is provided a method for preparing a hybrid resin capable of pyrolyzing and generating gas in a wide temperature range, the preparation method comprising: heating an organic resin, and then adding a MAX phase component and / or an inorganic ceramic component and mixing them to carry out a thermal polymerization reaction to obtain a hybrid resin;

[0015] wherein the inorganic ceramic component is selected from an oxide ceramic component and / or a non-oxide ceramic component;

[0016] wherein, based on 100 parts by mass of the organic resin, the amount of the MAX phase component is 0 - 100 parts by mass, the amount of the inorganic ceramic component is 0 - 100 parts by mass, and the amounts of the MAX phase component and the inorganic ceramic component are not both 0 at the same time.

[0017] In a fourth aspect of the present invention, there is provided an application of the hybrid resin provided in the second aspect, or the hybrid resin prepared by the preparation method provided in the third aspect, in a fiber-reinforced high-temperature resistant composite material.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] (1) The hybrid resin composition provided by the present invention includes an organic resin, a MAX phase component and / or an inorganic ceramic component, and it is defined that the inorganic ceramic component is selected from an oxide ceramic component and / or a non-oxide ceramic component, and by subjecting the hybrid resin composition to a thermal polymerization reaction, a hybrid resin capable of pyrolyzing in a wide temperature range, having high temperature resistance, oxidation resistance, and high residual carbon is constructed. Specifically, by using gradient design and physical and chemical effects such as melting, quasi-eutectic reaction, and carbothermal reduction reaction between components at high temperature, the self-repairing and self-strengthening capabilities of the hybrid resin are improved, and the overall temperature resistance level and erosion resistance performance of the hybrid resin are enhanced;

[0020] (2) The composition of the hybrid resin group provided by the present invention has strong designability, different MAX phases and inorganic ceramic components can be selected according to specific application environment requirements to adapt to different temperature and oxidation environment requirements, and it has the advantages of simple preparation process, strong operability, low manufacturing cost, good process applicability, being convenient for industrial batch preparation, and being easy to be promoted to applications;

[0021] (3) The hybrid resin provided by the present invention has the characteristics of being pyrolyzable in a wide temperature range, high temperature resistance, oxidation resistance, and self-reinforcement, and can be widely used in fiber-reinforced high-temperature composite materials, especially in ablative resin matrices that generate gas during pyrolysis in a wide temperature range. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the rheological curve of the hybrid resin S4 prepared in Example 4;

[0023] Figure 2 is a physical photo of the resin film prepared from the hybrid resin S4 prepared in Example 4 by the dry melt molding process (RFI);

[0024] Figure 3 is the DSC curve of the hybrid resin S4 prepared in Example 4;

[0025] Figure 4 are the TGA and DTG curves of the hybrid resin S4 prepared in Example 4 and the hybrid resins DS1-DS2 prepared in Comparative Examples 1-2;

[0026] Figure 5 is the release curve of benzene and phenol volatile organic compounds generated by pyrolysis of the hybrid resin S4 prepared in Example 4 and the hybrid resins DS1-DS2 prepared in Comparative Examples 1-2;

[0027] Figure 6 is the change curve of CO gas generated by pyrolysis of the hybrid resin S4 prepared in Example 4 and the hybrid resins DS1-DS2 prepared in Comparative Examples 1-2 with pyrolysis temperature;

[0028] Figure 7 is the XRD curve of carbide samples prepared from the hybrid resin S4 prepared in Example 4 and the hybrid resin DS2 prepared in Comparative Example 2 at different temperatures: (a) 600 °C; (b) 800 °C; (c) 1000 °C; (d) 1200 °C; (e) 1400 °C. DETAILED DESCRIPTION OF THE INVENTION

[0029] The endpoints and any values disclosed herein are not limited to the exact 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 each range, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0030] In the first aspect of the present invention, a hybrid resin composition capable of pyrolyzing and generating gas in a wide temperature range is provided. The hybrid resin composition includes: an organic resin, a MAX phase component, and / or an inorganic ceramic component, wherein the inorganic ceramic component is selected from an oxide ceramic component and / or a non-oxide ceramic component;

[0031] Wherein, based on 100 parts by mass of the organic resin, the dosage of the MAX phase component is 0-100 parts by mass, the dosage of the inorganic ceramic component is 0-100 parts by mass, and the dosages of the MAX phase component and the inorganic ceramic component are not both 0 at the same time.

[0032] The inventors of the present invention have found through research that: aiming at the problem that the heat protection effect of the matrix resin of traditional heat protection composites in the high-temperature stage (above 900 °C) urgently needs to be improved due to mass ejection and air flow blockage effects, the present invention first proposes to carry out the composition and structure design of hybrid resins from the perspective of the pyrolysis gas generation behavior of organic resins, provides a method for regulating the high-temperature pyrolysis gas generation behavior of organic resins, and provides a feasible new approach for the composition design and system construction of a wide-temperature-range pyrolytic hybrid resin system.

[0033] At the same time, adding an inorganic ceramic component, especially an oxide ceramic component, to the organic resin, and further pyrolyzing and generating gas by means of the carbothermal reduction reaction between the carbon formed by the organic resin and the oxide ceramic component at high temperature to improve the heat protection effect of the hybrid resin; adding a MAX phase component and a non-oxide ceramic component to the organic resin to improve the high-temperature resistance and oxidation resistance of the hybrid resin; introducing a MAX phase component, an oxide ceramic component, and a non-oxide ceramic component into the organic resin at the same time, and improving the temperature resistance grade and erosion resistance of the hybrid resin by enhancing the self-repairing and self-strengthening abilities of the hybrid resin.

[0034] In the present invention, unless otherwise specified, the hybrid resin composition includes: an organic resin, a MAX phase component, and / or an inorganic ceramic component, wherein the inorganic ceramic component is selected from an oxide ceramic component and / or a non-oxide ceramic component means that the hybrid resin composition includes an organic resin and a MAX phase component; or, includes an organic resin and an oxide ceramic component; or, includes an organic resin and a non-oxide ceramic component; or, includes an organic resin, an oxide ceramic component, and a non-oxide ceramic component; or, includes an organic resin, a MAX phase component, and an oxide ceramic component; or, includes an organic resin, a MAX phase component, and a non-oxide ceramic component; or, includes an organic resin, a MAX phase component, a non-oxide ceramic component, and an oxide ceramic component.

[0035] In some embodiments of the present invention, preferably, based on 100 parts by mass of the organic resin, the dosage of the MAX phase component is 0-50 parts by mass, the dosage of the inorganic ceramic component is 0-30 parts by mass, and the dosages of each component are not both 0 at the same time.

[0036] In some embodiments of the present invention, further preferably, based on 100 parts by mass of the organic resin, the dosage of the MAX phase component is 0-50 parts by mass, the dosage of the oxide ceramic component is 0-30 parts by mass, the dosage of the non-oxide ceramic component is 0-50 parts by mass, and the dosages of each component are not all 0 at the same time.

[0037] In some embodiments of the present invention, preferably, the solid content of the organic resin is 60-98 wt%, for example, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 90 wt%, 93.5 wt%, 98 wt%, and any value within the range composed of any two numerical values, preferably 65-93.5 wt%. In the present invention, the solid content parameter is obtained by testing according to GJB1059.1A-2020.

[0038] In some embodiments of the present invention, preferably, the rotational viscosity of the organic resin at 70 °C is 100-2000 mPa·s, for example, 100 mPa·s, 300 mPa·s, 400 mPa·s, 500 mPa·s, 650 mPa·s, 800 mPa·s, 1050 mPa·s, 1200 mPa·s, 1500 mPa·s, 2000 mPa·s, and any value within the range composed of any two numerical values, preferably 300-1200 mPa·s. In the present invention, the rotational viscosity parameter is obtained by the rotational viscosity test method (refer to GJB1059.2A-2020).

[0039] In the present invention, there is a wide selection range for the type of the organic resin, as long as the organic resin meets the above limitations. Preferably, the organic resin is selected from phenolic resin and / or silicone resin.

[0040] In some embodiments of the present invention, further preferably, the phenolic resin is selected from at least one of barium phenolic resin, amino phenolic resin, boron phenolic resin, sodium phenolic resin, boron-silicon hybrid phenolic resin, magnesium phenolic resin and thermoplastic phenolic resin; the silicone resin is selected from at least one of methyl silicone resin, phenyl silicone resin and vinyl phenyl silicone resin.

[0041] In some embodiments of the present invention, preferably, the MAX phase component is selected from at least one of Ti3AlC2, Ti3SiC2, Ti2SnC, V2AlC and Nb2AlC.

[0042] In the present invention, there is a wide selection range for the average particle size of the MAX phase component. Preferably, the average particle size of the MAX phase component is 0.1-50 μm.

[0043] In some embodiments of the present invention, preferably, based on 100 parts by mass of the organic resin, the MAX phase component includes: 0 - 50 parts by mass of Ti3AlC2, 0 - 30 parts by mass of Ti3SiC2, 0 - 30 parts by mass of Ti2SnC, 0 - 30 parts by mass of V2AlC, and 0 - 30 parts by mass of Nb2AlC, and the amounts of each component are not all 0 at the same time.

[0044] In some embodiments of the present invention, more preferably, based on 100 parts by mass of the organic resin, the MAX phase component includes: 10 - 50 parts by mass of Ti3AlC2, 10 - 30 parts by mass of Ti3SiC2, 10 - 30 parts by mass of Ti2SnC, 5 - 30 parts by mass of V2AlC, and 0 - 20 parts by mass of Nb2AlC.

[0045] In the present invention, without special instructions, the components of the inorganic ceramic component can also be defined according to the service requirements of the heat resistance grade for the hybridization.

[0046] In some embodiments of the present invention, the average particle size of the inorganic ceramic component is 0.1 - 50 μm. That is, the average particle sizes of the oxide ceramic component and the non-oxide ceramic component are each independently 0.1 - 50 μm.

[0047] In some embodiments of the present invention, preferably, the oxide ceramic component is selected from at least one of silicon oxide, boron oxide, aluminum oxide, zirconium oxide, and low-melting-point glass powder. In the present invention, the starting softening temperature of the low-melting-point glass powder is 350 - 650 °C.

[0048] In some embodiments of the present invention, preferably, based on 100 parts by mass of the organic resin, the oxide ceramic component includes: 0 - 20 parts by mass of silicon oxide, 0 - 20 parts by mass of boron oxide, 0 - 30 parts by mass of aluminum oxide, 0 - 45 parts by mass of zirconium oxide, and 0 - 30 parts by mass of low-melting-point glass powder, and the amounts of each component are not all 0 at the same time.

[0049] In some embodiments of the present invention, more preferably, based on 100 parts by mass of the organic resin, the oxide ceramic component includes: 10 - 20 parts by mass of silicon oxide, 10 - 20 parts by mass of boron oxide, 10 - 30 parts by mass of aluminum oxide, 25 - 45 parts by mass of zirconium oxide, and 5 - 15 parts by mass of low-melting-point glass powder.

[0050] In some embodiments of the present invention, preferably, the non-oxide ceramic component is selected from at least one of boron carbide, silicon carbide, zirconium carbide, hafnium carbide, tantalum carbide, zirconium diboride, titanium diboride, and elemental boron powder.

[0051] In some embodiments of the present invention, preferably, based on 100 parts by mass of the organic resin, the non-oxide ceramic components include: 0-30 parts by mass of boron carbide, 0-30 parts by mass of silicon carbide, 0-30 parts by mass of zirconium carbide, 0-10 parts by mass of hafnium carbide, 0-20 parts by mass of tantalum carbide, 0-50 parts by mass of zirconium diboride, 0-30 parts by mass of titanium diboride, and 0-15 parts by mass of elemental boron powder, and the amounts of each component are not all 0 at the same time.

[0052] In some embodiments of the present invention, more preferably, based on 100 parts by mass of the organic resin, the non-oxide ceramic components include: 10-30 parts by mass of boron carbide, 10-30 parts by mass of silicon carbide, 0-10 parts by mass of zirconium carbide, 5-10 parts by mass of hafnium carbide, 10-20 parts by mass of tantalum carbide, 5-10 parts by mass of zirconium diboride, 0-10 parts by mass of titanium diboride, and 5-15 parts by mass of elemental boron powder.

[0053] The second aspect of the present invention provides a hybrid resin capable of pyrolyzing and generating gas in a wide temperature range, and the hybrid resin is prepared by a thermal polymerization reaction of the hybrid resin composition provided by the first aspect.

[0054] For the hybrid resin provided by the present invention, after adding the MAX phase component and / or the inorganic ceramic component to the organic resin with a specific solid content and a specific rotational viscosity, the rotational viscosity of the prepared hybrid resin capable of pyrolyzing and generating gas in a wide temperature range can reach 10-60 Pa·s at 75°C, which can meet the process requirements of the dry hot melt forming resin film. Moreover, the cured product of the hybrid resin has the advantages of good heat resistance, excellent thermal stability, and high mass retention rate. The TGA test results of the cured product show that the 5wt% weight loss temperature is above 320°C under a nitrogen atmosphere, and the mass retention rate at 900°C is not less than 75%. It can be used as a new type of high-performance composite resin matrix with high temperature resistance, oxidation resistance, and erosion resistance.

[0055] In some embodiments of the present invention, preferably, the solid content of the hybrid resin is ≥90wt%, preferably 92-99wt%, for example, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 98wt%, 99wt%, and any value within the range composed of any two values.

[0056] In some embodiments of the present invention, preferably, the gel time of the hybrid resin at 150°C is 100-600 s, for example, 100 s, 110 s, 150 s, 200 s, 300 s, 400 s, 450 s, 600 s, and any value within the range composed of any two values, preferably 110-450 s.

[0057] In some embodiments of the present invention, preferably, the rotational viscosity of the hybrid resin at 75°C is selected from 10-60 Pa·s, for example, 10 Pa·s, 20 Pa·s, 30 Pa·s, 40 Pa·s, 50 Pa·s, 60 Pa·s, and any value in the range consisting of any two values, preferably 20-60 Pa·s.

[0058] In some embodiments of the present invention, preferably, in a non-oxidizing atmosphere, in a TGA test of the hybrid resin, the 5wt% weight loss temperature is ≥320°C, and the mass retention rate at 900°C is ≥75%. In the present invention, the non-oxidizing atmosphere includes but is not limited to nitrogen atmosphere, helium atmosphere, argon atmosphere, etc.

[0059] In some embodiments of the present invention, preferably, below 1000° C., the end groups, side chains and part of the main chains of the organic resin in the hybrid resin are cracked to produce gas; above 1000° C., the components in the hybrid resin are cracked to produce gas through physical and chemical reactions.

[0060] In the present invention, the hybrid resin that can be cracked and gasified within a wide temperature range produces gas through the cracking of the organic resin end group, side chain and part of the main chain below 1000°C, and the carbide formed by the interaction between the MAX phase material and the carbon chain in the component undergoes an oxidation reaction, absorbs oxygen free radicals in the system, increases the low-temperature residual carbon rate, produces oxides, and improves the overall strength of the resin matrix; in the high-temperature stage, especially above 1000°C, by utilizing the physical and chemical effects such as melting, volatilization, sublimation, carbonization and carbon thermal reduction between the components at high temperature, gas components such as CO and CO2 are further generated, thereby improving the heat protection effect of the material's mass injection and airflow blocking effect; the hybrid resin also uses the reinforcing effect of the non-oxide ceramic component to improve the overall high temperature resistance and oxidation resistance of the material.

[0061] The third aspect of the present invention provides a method for preparing a hybrid resin capable of cracking and producing gas in a wide temperature range, the method comprising: heating an organic resin, adding a MAX phase component and / or an inorganic ceramic component, mixing and performing a thermal polymerization reaction to obtain a hybrid resin;

[0062] Wherein, the inorganic ceramic component is selected from oxide ceramic components and / or non-oxide ceramic components;

[0063] Wherein, based on 100 parts by mass of the organic resin, the amount of the MAX phase component is 0-100 parts by mass, the amount of the inorganic ceramic component is 0-100 parts by mass, and the amounts of the MAX phase component and the inorganic ceramic component are not 0 at the same time.

[0064] In the present invention, without special instructions, the types and physical property parameters of the organic resin, MAX phase component, and inorganic ceramic component all conform to the above limitations, and the present invention will not elaborate herein.

[0065] In the present invention, the heating is intended to heat the organic resin to have good fluidity. Preferably, the heating temperature is 40 - 100°C, for example, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, and any value within the range composed of any two of these values, preferably 50 - 90°C.

[0066] In the present invention, the mixing is intended to mix the organic resin, MAX phase component, and / or inorganic ceramic component evenly; the thermal polymerization reaction is intended to polymerize the mixture containing the organic resin, MAX phase component, and / or inorganic ceramic component to obtain a new hybrid resin with wide-temperature-range cracking resistance, high temperature resistance, and oxidation resistance.

[0067] In some embodiments of the present invention, preferably, the conditions for the thermal polymerization reaction include: the temperature is 40 - 100°C, preferably 50 - 90°C; the time is 0.1 - 2 h, preferably 0.5 - 1.5 h.

[0068] In the present invention, the preparation method further includes: rapidly cooling the product of the thermal polymerization reaction to obtain the hybrid resin.

[0069] The fourth aspect of the present invention provides an application of the hybrid resin provided in the second aspect, or the hybrid resin prepared by the preparation method provided in the third aspect, in fiber-reinforced high-temperature-resistant composite materials, especially in ablation-resistant resin matrices that crack and produce gas within a wide temperature range.

[0070] The hybrid resin system provided by the present invention can meet the usage requirements of the resin film infusion (RFI) process, can be used as a high-performance matrix resin for the manufacture of fiber-reinforced high-temperature-resistant composite materials, and is expected to provide a high-performance matrix material for the manufacture of high-performance thermal protection composite materials in high-tech fields such as China's aviation, aerospace, and national defense industries, and has good application prospects.

[0071] The present invention will be described in detail below through examples.

[0072] Barium phenolic resin is purchased as a commercially available product with the brand name FQ - 180 resin produced by the Institute of Chemistry, Chinese Academy of Sciences;

[0073] Amino phenolic resin is purchased as a commercially available product with the brand name PF - 601 resin produced by the Institute of Chemistry, Chinese Academy of Sciences;

[0074] Boron phenolic resin is purchased as a commercially available product with the brand name BPF resin produced by Bengbu High Temperature Resin Factory, Anhui;

[0075] The silicone boron phenolic resin was purchased as a commercially available product with the brand name of SPR resin produced by the Institute of Chemistry, Chinese Academy of Sciences;

[0076] The methyl silicone resin was purchased as a commercially available product with the brand name of IOTA 6070 produced by Anhui Aiyota Silicone Oil Co., Ltd.;

[0077] The phenyl silicone resin was purchased as a commercially available product with the brand name of IOTA 6153D produced by Anhui Aiyota Silicone Oil Co., Ltd.;

[0078] The phenyl vinyl silicone resin was purchased as a commercially available product with the brand name of IOTA 208 produced by Anhui Aiyota Silicone Oil Co., Ltd.

[0079] Example 1

[0080] 107 g of barium phenolic resin (solid content 93.5 wt%; rotational viscosity at 70 °C 1050 mPa·s) was added to a 500 mL three-necked flask, and the temperature was raised to 90 °C with stirring;

[0081] The MAX phase components included: 30 g of Ti3AlC2 (purity ≥ 98 wt%, average particle size 18 μm), 10 g of Ti3SiC2 (purity ≥ 98 wt%, average particle size 23 μm), 10 g of Ti2SnC (purity ≥ 98 wt%, average particle size 23 μm), 15 g of V2AlC (purity ≥ 98 wt%, average particle size 23 μm) and 5 g of Nb2AlC (purity ≥ 98 wt%, average particle size 23 μm), were added to the above materials, and stirred at high speed at 90 °C for 15 min;

[0082] The oxide ceramic components included: 20 g of alumina (purity ≥ 98 wt%, average particle size 200 nm), 10 g of boron oxide (purity ≥ 95 wt%, average particle size 18 μm) and 5 g of glass powder (softening point 350 °C, average particle size 30 μm), were added to the above materials, stirred at high speed for 30 min until the materials were evenly mixed, and the mixed system was poured into an aluminum foil box while it was hot and quickly cooled to obtain 206 g of a uniformly composed barium phenolic resin (BMY) hybridized with MAX phase and oxide ceramics as hybrid resin S1, which was sealed and stored frozen.

[0083] Among them, the solid content of the above hybrid resin S1 was tested to be 98.32 wt%, the gel time at 150 °C was 132 s, and the rotational viscosity at 75 °C was 45 Pa·s.

[0084] Example 2

[0085] 117 g of amino-phenolic resin (solid content: 85.3 wt%; rotational viscosity at 70 °C: 650 mPa·s) was added to a 500 mL three-necked flask, and the temperature was raised to 75 °C with stirring.

[0086] The MAX phase components including 30 g of Ti3SiC2 (purity ≥ 98 wt%, average particle size: 23 μm), 20 g of Ti2SnC (purity ≥ 98 wt%, average particle size: 23 μm), and 30 g of V2AlC (purity ≥ 98 wt%, average particle size: 23 μm) were added to the above material, and stirred at high speed at 80 °C for 20 min.

[0087] The oxide ceramic components including 20 g of silicon oxide (purity ≥ 98 wt%, average particle size: 200 nm), 10 g of aluminum oxide (purity ≥ 98 wt%, average particle size: 200 nm), and 30 g of glass powder (softening point: 350 °C, average particle size: 30 μm) were added to the above material, and stirred at high speed for 40 min until the material was evenly mixed. While it was still hot, the mixed system was poured into an aluminum foil box and quickly cooled to obtain 252 g of amino-phenolic resin (AMY) hybridized with MAX phase and oxide ceramics with uniform composition as hybrid resin S2, which was sealed and stored frozen.

[0088] Among them, the solid content of the above hybrid resin S2 was tested to be 96.5 wt%, the gel time at 150 °C was 112 s, and the rotational viscosity at 75 °C was 42 Pa·s.

[0089] Example 3

[0090] The above boron-phenolic resin (pale yellow block solid at 25 °C, rotational viscosity at 70 °C: 40 Pa·s) was formulated into an ethanol solution with a solid content of 65 wt%. 154 g of the above boron-phenolic resin solution was added to a 500 mL three-necked flask, and the temperature was raised to 50 °C with stirring.

[0091] The MAX phase components including 30 g of Ti2SnC (purity ≥ 98 wt%, average particle size: 23 μm) and 30 g of V2AlC (purity ≥ 98 wt%, average particle size: 23 μm) were added to the above material, and stirred at high speed at 60 °C for 20 min until the material was evenly mixed.

[0092] The oxide ceramic components include: 10 g of boron oxide (purity ≥ 95 wt%, average particle size is 18 μm), 15 g of alumina (purity ≥ 98 wt%, average particle size is 200 nm), 25 g of zirconia (purity ≥ 99 wt%, average particle size is 300 nm), and 15 g of glass powder (softening point is 650 °C, average particle size is 30 μm). Add the above materials, and stir at high speed at 60 °C for 30 min until the materials are evenly mixed;

[0093] The non-oxide ceramic components include: 30 g of boron carbide (purity ≥ 95 wt%, average particle size is 10 μm), 10 g of silicon carbide (purity ≥ 95 wt%, average particle size is 15 μm), 10 g of hafnium carbide (purity ≥ 98 wt%, average particle size is 15 μm), 10 g of tantalum carbide (purity ≥ 98 wt%, average particle size is 18 μm), and 15 g of elemental boron powder (purity ≥ 95 wt%, average particle size is 18 μm). Add the above materials, and stir at high speed at 60 °C for 30 min until the materials are evenly mixed. Then, pour the mixed system into an aluminum foil box while it is still hot and cool it quickly to obtain 345 g of a uniformly composed MAX phase and inorganic ceramic hybrid boron phenolic resin (BMYF) as hybrid resin S3, and seal and store it frozen.

[0094] Among them, the solid content of the above hybrid resin S3 is tested to be 96.8 wt%, the gel time at 150 °C is 136 s, and the rotational viscosity at 75 °C is 60 Pa·s.

[0095] Example 4

[0096] Add 130 g of silicon boron phenolic resin (orange-yellow viscous liquid at 25 °C; rotational viscosity at 70 °C is 400 mPa·s, solid content is 77 wt%) to a 500 mL three-necked flask, and heat up while stirring until the material temperature reaches 70 °C;

[0097] The MAX phase components include: 30 g of Ti3AlC2 (purity ≥ 98 wt%, average particle size is 23 μm) and 20 g of Nb2AlC (purity ≥ 98 wt%, average particle size is 23 μm). Add the above materials, and stir at high speed at 70 °C for 20 min until the materials are evenly mixed;

[0098] The oxide ceramic components include: 10 g of boron oxide (purity ≥ 95 wt%, average particle size is 18 μm) and 10 g of alumina (purity ≥ 98 wt%, average particle size is 200 nm). Add the above materials, and stir at high speed at 75 °C for 30 min until the materials are evenly mixed;

[0099] The non-oxide ceramic components include: 30 g of silicon carbide (purity ≥ 95 wt%, average particle size of 15 μm) and 50 g of zirconium diboride (purity ≥ 98 wt%, average particle size of 18 μm). Add them to the above materials, stir at high speed at 80 °C for 30 min until the materials are evenly mixed. Then, pour the mixed system into an aluminum foil box while it is still hot and quickly cool it to obtain 270 g of a silicon-boron phenolic resin (BSM) with a uniform composition of MAX phase and inorganic ceramic hybrid as hybrid resin S4, and store it sealed and frozen.

[0100] Among them, the solid content of the above hybrid resin S4 is tested to be 93.8 wt%, the gel time at 150 °C is 135 s, and the rotational viscosity at 75 °C is 20 Pa·s, indicating that the processing performance of the above hybrid resin S4 is good.

[0101] Example 5

[0102] The above methyl silicone resin is a solution with very good fluidity at 25 °C, and the tested solid content is 50 wt%; before use, it is concentrated by rotary evaporation to remove the solvent until the solid content is 65 wt%, and the rotational viscosity at 70 °C is 350 mPa·s; add 154 g of the above concentrated methyl silicone resin solution to a 500 mL three-necked flask, and heat it to 80 °C while stirring.

[0103] The MAX phase components include: 10 g of Ti3AlC2 (purity ≥ 98 wt%, average particle size of 18 μm), 10 g of Ti3SiC2 (purity ≥ 98 wt%, average particle size of 23 μm), 10 g of Ti2SnC (purity ≥ 98 wt%, average particle size of 23 μm), 5 g of V2AlC (purity ≥ 98 wt%, average particle size of 23 μm) and 5 g of Nb2AlC (purity ≥ 98 wt%, average particle size of 23 μm). Add them to the above materials, stir at high speed at 70 °C for 20 min until the materials are evenly mixed.

[0104] The oxide ceramic components include: 10 g of silicon oxide (purity ≥ 98 wt%, average particle size of 200 nm), 10 g of boron oxide (purity ≥ 95 wt%, average particle size of 18 μm) and 10 g of aluminum oxide (purity ≥ 98 wt%, average particle size of 200 nm). Add them to the above materials, stir at high speed at 75 °C for 30 min until the materials are evenly mixed.

[0105] The non-oxide ceramic components include: 10 g of boron carbide (purity ≥ 95 wt%, average particle size of 15 μm), 10 g of silicon carbide (purity ≥ 95 wt%, average particle size of 15 μm), 10 g of hafnium carbide (purity ≥ 98 wt%, average particle size of 18 μm), 10 g of zirconium diboride (purity ≥ 98 wt%, average particle size of 15 μm), and 15 g of elemental boron powder (purity ≥ 95 wt%, average particle size of 15 μm). Add the above materials, stir at high speed at 80 °C for 30 min until the materials are evenly mixed, and then pour the mixed system into an aluminum foil box while it is still hot and quickly cool it to obtain 262 g of a MAX phase and inorganic ceramic hybrid methyl silicone resin (MSM) with a uniform composition as the hybrid resin S5, and store it sealed and frozen.

[0106] Among them, the solid content of the above hybrid resin S5 was tested to be 93.8 wt%, the gel time at 150 °C was 252 s, and the rotational viscosity at 75 °C was 15 Pa·s.

[0107] Example 6

[0108] The above phenyl silicone resin is a solution with very good fluidity at 25 °C, and the tested solid content is 51 wt%; before use, it is concentrated by rotary evaporation to remove the solvent until the solid content is 65 wt%, and the rotational viscosity at 70 °C is 550 mPa·s; add 308 g of the above concentrated phenyl silicone resin solution to a 1000 mL three-necked flask, and while stirring, heat up to the material temperature of 85 °C;

[0109] The MAX phase components include: 50 g of Ti3AlC2 (purity ≥ 98 wt%, average particle size of 18 μm), 20 g of Ti3SiC2 (purity ≥ 98 wt%, average particle size of 23 μm), 20 g of V2AlC (purity ≥ 98 wt%, average particle size of 23 μm), and 10 g of Nb2AlC (purity ≥ 98 wt%, average particle size of 23 μm). Add the above materials, stir at high speed at 85 °C for 20 min until the materials are evenly mixed;

[0110] The oxide ceramic components include: 20 g of boron oxide (purity ≥ 95 wt%, average particle size of 18 μm), 20 g of alumina (purity ≥ 98 wt%, average particle size of 200 nm), and 40 g of zirconia (purity ≥ 98 wt%, average particle size of 300 nm). Add the above materials, stir at high speed at 75 °C for 30 min until the materials are evenly mixed;

[0111] The non-oxide ceramic components include: 30 g of silicon carbide (purity ≥ 95 wt%, average particle size of 15 μm), 10 g of hafnium carbide (purity ≥ 98 wt%, average particle size of 15 μm), 10 g of zirconium diboride (purity ≥ 98 wt%, average particle size of 15 μm), 20 g of tantalum carbide (purity ≥ 98 wt%, average particle size of 18 μm), and 10 g of elemental boron powder (purity ≥ 95 wt%, average particle size of 18 μm). Add the above materials, stir at high speed at 90 °C for 30 min until the materials are evenly mixed, and pour the mixed system into an aluminum foil box while it is hot, and quickly cool it to obtain 552 g of a uniformly composed MAX phase and inorganic ceramic hybrid phenyl silicone resin (BSC) as hybrid resin S6, and store it sealed and frozen.

[0112] Among them, the solid content of the above hybrid resin S6 is tested to be 92.3 wt%, the gel time at 150 °C is 306 s, and the rotational viscosity at 75 °C is 25 Pa·s.

[0113] Example 7

[0114] The above phenyl vinyl silicone resin is a colorless transparent liquid at 25 °C, the tested solid content is 90 wt%, and the rotational viscosity at 70 °C is 320 mPa·s; add 150 g of the above phenyl vinyl silicone resin solution to a 500 mL three-necked flask, and heat up to 80 °C while stirring.

[0115] The oxide ceramic components include: 15 g of boron oxide (purity ≥ 95 wt%, average particle size of 18 μm), 30 g of alumina (purity ≥ 98 wt%, average particle size of 200 nm), and 45 g of zirconia (purity ≥ 98 wt%, average particle size of 300 nm). Add the above materials, stir at high speed at 80 °C for 30 min until the materials are evenly mixed.

[0116] The non-oxide ceramic components include: 15 g of silicon carbide (purity ≥ 95 wt%, average particle size of 15 μm), 7.5 g of hafnium carbide (purity ≥ 98 wt%, average particle size of 15 μm), 7.5 g of zirconium diboride (purity ≥ 98 wt%, average particle size of 15 μm), 15 g of tantalum carbide (purity ≥ 98 wt%, average particle size of 18 μm), and 7.5 g of elemental boron powder (purity ≥ 95 wt%, average particle size of 18 μm). Add the above materials, stir at high speed at 85 °C for 30 min until the materials are evenly mixed, and pour the mixed system into an aluminum foil box while it is hot, and quickly cool it to obtain 552 g of a uniformly composed inorganic ceramic hybrid phenyl vinyl silicone resin (YSC) as hybrid resin S7, and store it sealed and frozen.

[0117] Among them, the solid content of the hybrid resin S7 was tested to be 93.4 wt%, the gel time at 150 °C was 426 s, and the rotational viscosity at 75 °C was 16 Pa·s.

[0118] Comparative Example 1

[0119] Directly use the barium phenolic resin in Example 1 as the hybrid resin DS1.

[0120] Comparative Example 2

[0121] Directly use the silicon boron phenolic resin in Example 4 as the hybrid resin DS2.

[0122] Test Example

[0123] Rotational Viscosity Test: The rotational viscosity of the resin was tested using the rotational viscosity test method (refer to GJB 1059.2A-2020), and the test instrument was an NDJ-9 type rotational viscometer.

[0124] Rheological Property Test: The test was carried out using an AR2000 type rheometer from TA Company. The temperature range for testing the change of rotational viscosity with temperature was 50 - 150 °C, and the heating rate was 5 °C / min; the change of the viscosity of the resin with temperature was tested to evaluate the width and narrowness of its processing window.

[0125] Preparation Conditions of Resin Cured Product: 120 °C / 2 h → 140 °C / 2 h → 160 °C / 2 h → 180 °C / 4 h, and the heating-up time between temperature segments was 30 minutes.

[0126] Curing Behavior Test: Differential scanning calorimetry (DSC) test was carried out using a Mettler Toledo DSC 822e type differential scanning calorimeter. With N2 as the test atmosphere, the flow rate was 50 mL / min, the heating rate was 20 °C / min, and the test range was 30 - 350 °C.

[0127] Test Conditions for Thermogravimetry-Infrared-Mass Spectrometry Coupling: Argon atmosphere, the sample was heated to 1500 °C at a rate of 10 °C / min, the mass spectrometry scanning time interval was 30 s, and the scanning mass-to-charge ratio (m / z) range was 10 - 250.

[0128] Preparation Conditions of Resin Carbide: Using a tubular furnace of model GSL-16000Y, argon atmosphere, heating to the target temperature at a rate of 10 °C / min, and then holding for 2 hours; the target temperatures were 600 °C, 800 °C, 1000 °C, 1200 °C, and 1400 °C respectively.

[0129] XRD analysis: At room temperature, the zirconium diboride / SiC ceramic matrix composite reinforced with carbon fiber based on CPF-4 resin was tested on a D / MAX-2400 X-ray diffractometer produced by Shimadzu Corporation, Japan; CuKα radiation source was used, with an emission voltage of 40 kV and a current of 200 mA. The test scanning angle range was 3 - 80°, and the scanning speed was 8° / min.

[0130] (1) The rheological curve of the hybrid resin S4 prepared in Example 4 is as shown in Figure 1 . It can be seen from Figure 1 that as the test temperature increases, the viscosity of the hybrid resin S4 gradually decreases. When the temperature rises to 90 °C, the viscosity of the hybrid resin S4 drops below 10 Pa·s; at 110 °C, the viscosity of the hybrid resin S4 reaches a minimum of about 5 Pa·s. At this time, the hybrid resin S4 has good wettability, which is very beneficial for the preparation of high-quality composites. When the temperature further rises above 135 °C, the viscosity of the hybrid resin S4 increases sharply, indicating that the resin gel reaction accelerates. However, from the overall state of the rheological curve of the hybrid resin S4, the viscosity is relatively low in the range of 90 - 135 °C, and its process window is relatively wide.

[0131] (2) The physical picture of the resin film prepared from the hybrid resin S4 obtained in Example 4 by the dry melt molding process (RFI) is as shown in Figure 2 . It can be seen from Figure 2 that when using the hot melt process to prepare the resin film of the hybrid resin S4, its areal density is 400 g / m 2 ; The practical results show that the hybrid resin S4 has excellent process performance and can meet the usage requirements of the melt molding process for manufacturing resin films.

[0132] (3) The curing performance of the hybrid resin S4 was studied using a differential scanning calorimeter (DSC). The DSC curve of the hybrid resin S4 prepared in Example 4 is as shown in Figure 3 . It can be seen from Figure 3 that the curing temperature range of the hybrid resin S4 is between 150 - 300 °C, and its curing reaction peak temperature is 188.32 °C, indicating that the curing exothermic temperature range of this hybrid resin S4 is wide, and the curing reaction exotherm is 141.23 J / g, and the heat release is not large, indicating that this hybrid resin S4 has excellent curing process performance.

[0133] (4) The pyrolysis behavior of the hybrid resin S4 prepared in Example 4 and the hybrid resins DS1 - DS2 prepared in Comparative Examples 1 - 2 and the release of pyrolysis gases were characterized using thermogravimetric infrared spectroscopy mass spectrometry (TG-IR-MS). The results are as shown in Figure 4 and Table 1.

[0134] Table 1

[0135]

[0136] Based on Figure 4 and the data in Table 1, it can be seen that as the test temperature increases, the hybrid resin DS1 (i.e., traditional phenolic resin) decomposes the fastest. Its mass retention rate at 400 °C is 95%, and the mass retention rate at 700 °C is 66%. The weight loss rate between 400 - 700 °C is 29%. However, when the temperature rises above 900 °C, its mass retention rate remains basically unchanged, indicating that the decomposition to produce gas is basically over, and the mass entrainment and gas flow blocking effects as the matrix material of the thermal protection composite material no longer play a role in thermal protection. In comparison, as the test temperature increases, the hybrid resin DS2 (borosilicate hybrid phenolic) and the hybrid resin S4 show obvious decomposition behavior in the range of 150 - 700 °C. The weight loss rates in the temperature range of 400 - 700 °C are 16% and 17% respectively, which are similar. And as the temperature further increases, they will still slowly lose weight. Especially when the temperature rises above 1100 °C, a relatively rapid decomposition occurs. The weight loss rate of the hybrid resin DS2 in the range of 1100 - 1550 °C is 13%, while the corresponding weight loss rate of the hybrid resin S4 reaches 26%, indicating that the gas production reaction of the matrix resin continues, and the thermal protection effect of its mass entrainment and gas flow blocking effects is still obvious, showing that the hybrid resin S4 has the characteristic of pyrolyzing and producing gas in a wide temperature range, verifying that the method proposed in the present invention for regulating the high-temperature pyrolysis gas production behavior of organic resins is effective.

[0137] Meanwhile, by comparing Figure 4 the TGA curves of the hybrid resin S4 prepared in Example 4 and the hybrid resins DS1 - DS2 prepared in Comparative Examples 1 - 2, it can be seen that when the temperature rises to 700 °C, the mass retention rate of the hybrid resin S4 is close to 80%, the mass retention rate of the hybrid resin DS2 is about 75%, and that of the hybrid resin DS1 is 63%, indicating that the hybrid resin S4 has excellent high-temperature resistance.

[0138] By further comparing Figure 4 the DTG curves of the hybrid resin S4 prepared in Example 4 and the hybrid resins DS1 - DS2 prepared in Comparative Examples 1 - 2, it can be seen that the hybrid resin DS1 has a single-peak decomposition, and its maximum thermal decomposition temperature is around 500 °C, and there is no thermal decomposition peak at higher temperatures; the hybrid resin DS2 has thermal decomposition peaks at 600 °C and 1450 °C respectively, while the hybrid resin S4 has two obvious thermal decomposition peaks in the ranges of 375 - 650 °C and 1100 - 1500 °C respectively, and the second thermal decomposition peak is more obvious, indicating that it can decompose and produce gas in a wider temperature range, also verifying the effectiveness of the material system design of the present invention.

[0139] (5) The release curves of benzene - type and phenol - type volatile organic compounds generated by the pyrolysis of the hybrid resin S4 prepared in Example 4 and the hybrid resins DS1 - DS2 prepared in Comparative Examples 1 - 2 were characterized by thermogravimetry - infrared spectroscopy - mass spectrometry (TG - IR - MS). The results are as Figure 5 shown. It can be seen from Figure 5 that both the hybrid resin DS1, the hybrid resin DS2, and the hybrid resin S4 will release benzene - type organic compounds. The hybrid resin DS1 releases a relatively large variety of phenol - type volatile organic compounds, the hybrid resin DS2 also releases a small amount of phenol - type organic compounds, while no phenol - type volatile organic compounds were detected in the hybrid resin S4.

[0140] The reason for the above - mentioned mass spectrometry detection results is that the pyrolysis of the hybrid resin DS1 and the hybrid resin DS2 at 150 - 700 °C is mainly due to the cleavage of phenolic end - groups in the cross - linked structure of phenolic resin, resulting in the release of more phenol - type and benzene - type substances. Compared with the hybrid resin DS1 and the hybrid resin DS2, almost no phenolic derivatives were detected in the pyrolysis products of the hybrid resin S4 at 150 - 700 °C, and the derivation of organic benzene was also significantly lower. Therefore, the high - temperature mass retention rate of this resin is high, indicating that the introduction of the MAX phase and inorganic ceramic components in the material system plays a role in oxygen absorption and carbon fixation, which is very beneficial to improving the overall integrity of the material.

[0141] (6) The temperature - dependent curves of CO gas release produced by the pyrolysis of the hybrid resin S4 prepared in Example 4 and the hybrid resins DS1 - DS2 prepared in Comparative Examples 1 - 2 were characterized by thermogravimetry - infrared spectroscopy - mass spectrometry (TG - IR - MS). The results are as Figure 6 shown. It can be seen from Figure 6 that the CO gas produced by the pyrolysis of the hybrid resin DS1 is mainly in the temperature range of 150 - 800 °C; while the CO gas produced by the pyrolysis of the hybrid resin S4 is released in two temperature ranges, which are located at 150 - 800 °C and 1100 - 1500 °C respectively, indicating that the temperature range of pyrolysis gas production of the hybrid resin S4 system has been significantly broadened, which is very beneficial to improving the heat - insulation effect of the matrix material at high - temperature stages. Similarly, it can be seen that the temperature corresponding to the CO release peak in the CO release curve is consistent with the temperature corresponding to the thermal decomposition peak in the thermogravimetric curve.

[0142] (7) X - ray diffraction technology (XRD) was used to characterize the phases in the carbides formed after the hybrid resin S4 prepared in Example 4 and the hybrid resin DS2 prepared in Comparative Example 2 were heat - treated at 600 °C, 800 °C, 1000 °C, 1200 °C, and 1400 °C respectively, and the phase transformation process was explored. The results are as Figure 7(a)-7(e) shown, and the corresponding chemical reactions for the phases appearing at different temperatures are shown in Table 2, revealing the mechanism of high - temperature resistance and oxidation resistance of the resin prepared in this patent.

[0143] Table 2

[0144]

[0145] It can be seen from Figure 7(a)-7(e) that the TiC appearing at 600 °C is caused by the removal of aluminum element at high temperature of MAX, corresponding to reaction formula ①; the TiO2 appearing at 800 °C is generated by the reaction of TiC with oxygen in the system, corresponding to reaction formula ②; the Ti3O5 appearing at 1000 °C is produced by the carbothermal reduction of TiO2, corresponding to reaction formula ⑤; meanwhile, Al4B2O9 appears in the system at 1000 °C, corresponding to reaction formula ④, indicating that aluminum has the function of fixing boron; TiB2 and TiC appear at 1400 °C. The TiC is produced by the carbothermal reduction of SiO2, corresponding to reaction formula ⑨; TiB2 is obtained by the reaction of Ti3O5 with Al4B2O9 or B2O3, corresponding to reactions ⑦ and ⑧ respectively; at 1400 °C, the Si in the system undergoes a carbothermal reduction reaction, which is consistent with the CO release temperature corresponding to the hybrid resin DS2; the hybrid resin S4 doped with MAX phase shows the appearance of Ti3O5 at 1000 °C and starts to produce CO, which is consistent with the CO release temperature, and the temperature range is widened compared with traditional phenolic resin and borosilicate hybrid phenolic resin.

[0146] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A hybrid resin composition capable of pyrolyzing to produce gas in a wide temperature range, characterized in that, The hybrid resin composition includes: an organic resin, a MAX phase component, and / or an inorganic ceramic component, wherein the inorganic ceramic component is selected from an oxide ceramic component and / or a non-oxide ceramic component; Wherein, based on 100 parts by mass of the organic resin, the dosage of the MAX phase component is 0 - 100 parts by mass, the dosage of the inorganic ceramic component is 0 - 100 parts by mass, and the dosages of the MAX phase component and the inorganic ceramic component are not both 0 at the same time.

2. The hybrid resin composition according to claim 1, wherein Based on 100 parts by mass of the organic resin, the dosage of the MAX phase component is 0 - 50 parts by mass, the dosage of the inorganic ceramic component is 0 - 30 parts by mass, and the dosages of each component are not both 0 at the same time; Preferably, based on 100 parts by mass of the organic resin, the dosage of the MAX phase component is 0 - 50 parts by mass, the dosage of the oxide ceramic component is 0 - 30 parts by mass, the dosage of the non-oxide ceramic component is 0 - 50 parts by mass, and the dosages of each component are not both 0 at the same time.

3. The hybrid resin composition according to claim 1 or 2, wherein The solid content of the organic resin is 60 - 98 wt%, preferably 65 - 93.5 wt%; and / or, the rotational viscosity of the organic resin at 70 °C is 100 - 2000 mPa·s, preferably 300 - 1200 mPa·s; and / or, the organic resin is selected from phenolic resin and / or silicone resin, and the phenolic resin is selected from at least one of barium phenolic resin, amino phenolic resin, boron phenolic resin, sodium phenolic resin, boron-silicon hybrid phenolic resin, magnesium phenolic resin, and thermoplastic phenolic resin; the silicone resin is selected from at least one of methyl silicone resin, phenyl silicone resin, and vinyl phenyl silicone resin.

4. The hybrid resin composition according to any one of claims 1-3, wherein, The MAX phase component is selected from at least one of Ti3AlC2, Ti3SiC2, Ti2SnC, V2AlC, and Nb2AlC; Preferably, based on 100 parts by mass of the organic resin, the MAX phase component includes: 0 - 50 parts by mass of Ti3AlC2, 0 - 30 parts by mass of Ti3SiC2, 0 - 30 parts by mass of Ti2SnC, 0 - 30 parts by mass of V2AlC, and 0 - 30 parts by mass of Nb2AlC, and the dosages of each component are not both 0 at the same time; More preferably, based on 100 parts by mass of the organic resin, the MAX phase component includes: 10 - 50 parts by mass of Ti3AlC2, 10 - 30 parts by mass of Ti3SiC2, 10 - 30 parts by mass of Ti2SnC, 5 - 30 parts by mass of V2AlC, and 0 - 20 parts by mass of Nb2AlC.

5. The hybrid resin composition according to any one of claims 1-4, wherein The oxide ceramic component is selected from at least one of silicon oxide, boron oxide, aluminum oxide, zirconium oxide, and low melting point glass powder; Preferably, based on 100 parts by mass of the organic resin, the oxide ceramic component includes: 0 - 20 parts by mass of silicon oxide, 0 - 20 parts by mass of boron oxide, 0 - 30 parts by mass of aluminum oxide, 0 - 45 parts by mass of zirconium oxide, and 0 - 30 parts by mass of low melting point glass powder, and the dosages of each component are not both 0 at the same time; Further preferably, based on 100 parts by mass of the organic resin, the oxide ceramic component comprises: 10-20 parts by mass of silicon oxide, 10-20 parts by mass of boron oxide, 10-30 parts by mass of aluminum oxide, 25-45 parts by mass of zirconium oxide, and 5-15 parts by mass of low-melting-point glass powder; and / or, the non-oxide ceramic component is selected from at least one of boron carbide, silicon carbide, zirconium carbide, hafnium carbide, tantalum carbide, zirconium diboride, titanium diboride, and elemental boron powder; Preferably, based on 100 parts by mass of the organic resin, the non-oxide ceramic component comprises: 0-30 parts by mass of boron carbide, 0-30 parts by mass of silicon carbide, 0-30 parts by mass of zirconium carbide, 0-10 parts by mass of hafnium carbide, 0-20 parts by mass of tantalum carbide, 0-50 parts by mass of zirconium diboride, 0-30 parts by mass of titanium diboride, and 0-15 parts by mass of elemental boron powder, and the amounts of the components are not all 0 at the same time; Further preferably, based on 100 parts by mass of the organic resin, the non-oxide ceramic component comprises: 10-30 parts by mass of boron carbide, 10-30 parts by mass of silicon carbide, 0-10 parts by mass of zirconium carbide, 5-10 parts by mass of hafnium carbide, 10-20 parts by mass of tantalum carbide, 5-10 parts by mass of zirconium diboride, 0-10 parts by mass of titanium diboride, and 5-15 parts by mass of elemental boron powder.

6. A hybrid resin capable of pyrolyzing to produce gas in a wide temperature range, characterized in that, The hybrid resin is prepared by thermal polymerization of the hybrid resin composition according to any one of claims 1-5.

7. The hybrid resin according to claim 6, wherein, The solid content of the hybrid resin is ≥90 wt%, preferably 92-99 wt%; and / or, the gel time of the hybrid resin at 150 °C is 100-600 s, preferably 110-450 s; and / or, the rotational viscosity of the hybrid resin at 75 °C is selected from 10-60 Pa·s, preferably 20-60 Pa·s; and / or, in a non-oxidizing atmosphere, in the TGA test of the hybrid resin, the 5 wt% weight loss temperature ≥320 °C, and the mass retention rate at 900 °C ≥75%; and / or, when the temperature is below 1000 °C, the end groups, side chains, and part of the main chain of the organic resin in the hybrid resin crack to produce gas; when the temperature is above 1000 °C, the components in the hybrid resin undergo physical and chemical reactions to produce gas by cracking.

8. A preparation method of a hybrid resin capable of pyrolyzing to produce gas in a wide temperature range, characterized in that, The preparation method includes: heating the organic resin, then adding the MAX phase component and / or the inorganic ceramic component and mixing them for thermal polymerization reaction to obtain the hybrid resin; wherein, the inorganic ceramic component is selected from the oxide ceramic component and / or the non-oxide ceramic component; wherein, based on 100 parts by mass of the organic resin, the amount of the MAX phase component is 0-100 parts by mass, the amount of the inorganic ceramic component is 0-100 parts by mass, and the amounts of the MAX phase component and the inorganic ceramic component are not all 0 at the same time.

9. According to the preparation method described in claim 8, wherein The heating temperature is 40-100 °C, preferably 50-90 °C; and / or, the conditions of the thermal polymerization reaction include: the temperature is 40-100 °C, preferably 50-90 °C; the time is 0.1-2 h, preferably 0.5-1.5 h.

10. Use of the hybrid resin according to claim 6 or 7, or the hybrid resin prepared by the preparation method according to claim 8 or 9, in a matrix of a fiber-reinforced high-temperature resistant composite material, in particular in a charring gas-producing ablation-resistant resin matrix within a wide temperature range.

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