A carborane-hybridized rtm polyimide resin and a method for preparing the same

Abstract

The application belongs to the technical field of resin-based composite material manufacturing, and relates to a carborane hybrid RTM polyimide resin and a preparation method thereof. The carborane hybrid RTM polyimide resin comprises A component and B component. The A component is used for adjusting the viscosity and open period of the resin, and the B component is used for adjusting the strength and heat resistance of the resin. The A component is added into the high-concentration solution of the B component in the form of powder after completing imidization, the solvent is removed through vacuum low pressure, and then the cyclization process is completed through high-temperature solvent-free imidization reaction, so that the carborane hybrid RTM polyimide resin with low volatile content is obtained. The application adopts a composite structure, can ensure high heat resistance, and can obtain low viscosity and long open period at the same time. Meanwhile, the low-boiling-point solvent is used as a reaction solvent, so that the production efficiency can be significantly improved, and the process cost can be reduced.

Description

Technical Field

[0001] This invention belongs to the field of resin-based composite material manufacturing technology, and relates to a carborane hybrid RTM polyimide resin and its preparation method. Background Technology

[0002] With the rapid development of aerospace technology at home and abroad, the demand for high-temperature resistant complex parts and structures is becoming increasingly urgent. These complex structures are often difficult to achieve integral molding using traditional autoclave processes. Liquid-molded polyimide has already received widespread attention and application in the field of aero-engines due to its excellent performance characteristics. As early as the 1990s, NASA developed typical RTM-molded polyimide resin grades such as PETI-RTM, PETI-298, PETI-330, and PETI-375, and carried out a lot of application research. It has already begun to be verified and applied in engine structures.

[0003] However, with the development of aerospace equipment such as high-speed missiles and hypersonic vehicles, there is a clear demand for RTM-moldable polyimides that can withstand temperatures above 400°C. Typical PETI-type polyimide resins, such as PETI-375, have a pure organic molecular backbone, which is difficult to meet the requirements for long-term service at 400°C even through molecular structure optimization. Invention patents such as CN103881091A, CN104945627A, CN 110498923A, and CN 107459648A disclose polyimide resins containing carborane structures. These patents mainly use high-boiling-point solvents for synthesis, and the resulting polyimide resins often have high viscosity. When used in autoclave molding processes, they cannot meet the requirements of RTM processes for low viscosity and long open periods. Summary of the Invention

[0004] (a) Technical problems to be solved

[0005] The technical problem to be solved by the present invention is to improve the long-term temperature resistance of RTM polyimide resin to 400°C, while obtaining its lower viscosity and longer processing time to meet the application requirements of large-size complex high-temperature resistant structures.

[0006] (II) Technical Solution

[0007] To solve the above-mentioned technical problems, the present invention provides a carborane hybrid RTM polyimide resin, wherein the raw materials for preparing the carborane hybrid RTM polyimide resin include component A and component B;

[0008] Component A comprises the structure shown in Formula I:

[0009]

[0010] Formula I;

[0011] Component B comprises the structure shown in Formula II:

[0012]

[0013] Formula II

[0014] In Formula II, X1 represents any of the following substituents:

[0015] , , , , , , ,

[0016] , ,

[0017] ,

[0018] n is 0, 1, or 2.

[0019] This invention also provides a method for preparing component A as follows:

[0020] S1.1 Dissolve 4-phenylacetylene phthalic anhydride in an alcohol solvent and react to obtain an esterified solution;

[0021] S1.2 Dissolve the carborane diamine monomer in an organic solvent and heat under inert gas protection to obtain a diamine solution;

[0022] S1.3 The esterification solution and the diamine solution are mixed to carry out a polymerization reaction to obtain a resin solution;

[0023] S1.4 The resin solution is heated and reacted under vacuum, and then cooled to obtain a block resin containing a compound with the structure shown in Formula I.

[0024] The block resin described in S1.5 is pulverized to obtain component A;

[0025] Component A is a resin powder with a particle size of 50-200 mesh.

[0026] In a preferred embodiment of the present invention, in step S1.1, the reaction temperature is 60℃-90℃, the reaction time is 1h-4h, and the concentration of the esterification solution obtained by the reaction is 20wt%-80wt%.

[0027] In a preferred embodiment of the present invention, in step S1.2, the heating temperature is 40℃-80℃, and the concentration of the diamine solution obtained by heating is 20wt%-80wt%.

[0028] In a preferred embodiment of the present invention, step S1.3 includes the following steps: pouring the esterification solution into the diamine solution, heating to 60°C-80°C under stirring for 1-5 hours of polymerization; then heating to 80-120°C, controlling the vacuum degree to ≤-0.09MPa, and reacting for 1-12 hours to obtain the resin solution.

[0029] In a preferred embodiment of the present invention, in step S1.4, the temperature for heating is 150℃-260℃, and the reaction time under vacuum is 1h-6h.

[0030] This invention also provides a method for preparing component B as follows:

[0031] S2.1 Dissolve 4-phenylacetylene phthalic anhydride and 2,3,3',4'-biphenyltetraic dianhydride monomers in an alcohol solvent and react to obtain an esterified solution;

[0032] S2.2 Dissolve the diamine monomer and carborane diamine monomer in an organic solvent, and heat under an inert gas to obtain a mixed diamine solution;

[0033] S2.3 The esterification solution is poured into the mixed diamine solution, and a polymerization reaction is carried out to obtain a resin solution containing a compound with the structure shown in Formula II, i.e., component B.

[0034] In a preferred embodiment of the present invention, the mass percentage content of the compound with the structure shown in Formula II in component B is 60wt%-90wt%.

[0035] In a preferred embodiment of the present invention, in step S2.1, the reaction temperature is 60℃-90℃, the reaction time is 1h-6h, and the concentration of the obtained esterification solution is 20wt%-80wt%.

[0036] In a preferred embodiment of the present invention, in step S2.2, the heating temperature is 40℃-60℃, and the concentration of the mixed diamine solution obtained by heating is 20wt%-80wt%.

[0037] In a preferred embodiment of the present invention, step S2.3 includes the following steps: pouring the esterification solution into the mixed diamine solution, heating to 60°C-80°C under stirring for 1-5 hours; then heating to 80-120°C, maintaining a vacuum of ≤-0.09MPa, and reacting for 1-12 hours to obtain component B.

[0038] The diamine monomer used in this invention is selected from one or two of m-PDA, 3,4-ODA, TFMBZ, 1,3,4-APB, 4,4-MDA, 4,4-DDS, p-ODA, BAPP, and FDA.

[0039] The organic solvent used in this invention is one or a mixture of several of the following: alcohol solvents, tetrahydrofuran, dioxane, N,N-dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone.

[0040] The alcohol solvent used in this invention is one or a mixture of several of methanol, ethanol, propanol, isopropanol, butanol, and n-butanol in any proportion.

[0041] This invention also provides a method for preparing carborane hybrid RTM polyimide resin, comprising the steps of:

[0042] S1. Heat component B to a first temperature, add component A to it, stir, then sonicate, then heat to a second temperature, perform a vacuum reaction, and then cool to obtain blocky carborane hybrid RTM polyimide resin;

[0043] S2. The blocky carborane hybrid RTM polyimide resin is pulverized to obtain powdered carborane hybrid RTM polyimide resin.

[0044] In a preferred embodiment of the present invention, the first temperature is 90-120°C and the second temperature is 150°C-260°C.

[0045] In a preferred embodiment of the present invention, in step S1, the reaction time of the vacuum reaction is 1h-6h.

[0046] In a preferred embodiment of the present invention, in step S2, the particle size of the powdered carborane hybrid RTM polyimide resin is ≥20 mesh.

[0047] In a preferred embodiment of the present invention, the content of component A accounts for 10% to 90% of the total content of component A and component B.

[0048] The unremoved solvent volatile content of the carborane hybrid RTM polyimide resin is ≤1%.

[0049] This invention also provides an application of carborane hybrid RTM polyimide resin in RTM, VARTM, VARI, and RFI molding.

[0050] (III) Beneficial Effects

[0051] The above-described technical solution of the present invention has the following advantages:

[0052] 1. The carborane hybrid RTM polyimide resin of the present invention is composed of component A and component B, which are compounded in a certain proportion. Component A is used to adjust the resin viscosity and open period, and component B is used to adjust the resin strength and heat resistance. Component A is added to a high-concentration solution of component B in the form of an imidized powder. Then, the polymerization solvent is removed by a vacuum low-pressure polymerization reaction, and then the cyclization process is completed by a high-temperature solventless imidization reaction to obtain a carborane hybrid RTM polyimide resin with low volatile content.

[0053] 2. The carborane hybrid RTM polyimide resin of this invention adopts a composite structure, which can achieve low viscosity and long open period while ensuring high resistance. Furthermore, the use of a low-boiling-point solvent as the reaction solvent can significantly improve production efficiency and reduce process costs. It also avoids the use of large amounts of toxic high-boiling-point solvents during the polymerization reaction and the use of large amounts of volatile solvents during washing and powdering, significantly reducing the environmental pollution caused by these solvents. Detailed Implementation

[0054] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[0055] Preparation Example 1

[0056] This preparation example provides a powdered resin of component A, the preparation method of which includes the following steps:

[0057] S1. Dissolve 3016.49g of 4-phenylacetylene phthalic anhydride in 4530g of ethanol solvent and reflux at 78℃ for 4h to obtain an esterification solution with a concentration of 40wt%.

[0058] S2. Dissolve 1983.51g of carborane diamine monomer in 4630g of ethanol solvent, heat to 50℃ under inert gas protection, and stir for 0.5h to obtain a diamine solution with a concentration of 30wt%.

[0059] S3. Pour the esterification solution obtained above into the diamine solution, and heat it to 78°C for 5 hours under stirring in the reaction vessel; then heat it to 90°C while applying a continuous vacuum to the reaction vessel with a vacuum degree ≤ -0.09 MPa for 6 hours. The organic solvents volatilized or generated during the reaction are collected using a special solvent recovery device to obtain a resin solution.

[0060] S4. Heat the reaction vessel to 200°C and react under vacuum for 5 hours. After natural cooling, obtain blocky component A resin.

[0061] S5. The above-obtained block resin is mechanically pulverized using a pulverizer, and the particle size of the pulverized resin is controlled to be 150-200 mesh to obtain component A powder resin, i.e., component A.

[0062] The structural formula of component A is as follows:

[0063]

[0064] Table 1 Basic Properties of Component A Resin

[0065]

[0066] Preparation Example 2

[0067] This preparation example provides a powdered resin of component A, the preparation method of which includes the following steps:

[0068] S1. Dissolve 3016.49g of 4-phenylacetylene phthalic anhydride in 4530g of ethanol solvent and reflux at 78℃ for 3h to obtain an esterification solution with a concentration of 40wt%.

[0069] S2. Dissolve 1983.51g of carborane diamine monomer in 4630g of dioxane, heat to 60℃ under inert gas protection, and stir for 1h to obtain a diamine solution with a concentration of 30wt%.

[0070] S3. Pour the esterification solution obtained above into the diamine solution, and heat it to 75°C for 4 hours under stirring in the reaction vessel; then heat it to 100°C while applying a continuous vacuum to the reaction vessel with a vacuum degree ≤ -0.09MPa for 5 hours. The organic solvents volatilized or generated during the reaction are collected using a special solvent recovery device to obtain a resin solution.

[0071] S4. Heat the reaction vessel to 250°C and react under vacuum for 6 hours. After natural cooling, obtain blocky component A resin.

[0072] S5. The above-obtained block resin is mechanically pulverized using a pulverizer, and the particle size of the pulverized resin is controlled to be 150-200 mesh to obtain component A powder resin, i.e., component A.

[0073] Table 2 Basic Properties of Component A Resin

[0074]

[0075] Preparation Example 3

[0076] This preparation example provides a component B solution, the preparation method of which includes the following steps:

[0077] S1. Dissolve 2025g of 4-phenylacetylene phthalic anhydride and 1200g of 2,3,3',4'-biphenyltetraic dianhydride monomer in 4839g of ethanol, and reflux at 80℃ for 4h to obtain an esterification solution with a concentration of 40wt%.

[0078] S2. Dissolve 440g of m-phenylenediamine and 1330g of diaminophenylcarboroline diamine monomer in 4138g of ethanol solvent, and heat to 55℃ under inert gas protection to obtain a diamine solution with a concentration of 30wt%.

[0079] S3. Pour the esterification solution obtained above into the diamine solution, and heat it to 78°C for 4 hours under stirring in the reaction vessel; further heat it to 95°C, and at the same time apply a continuous vacuum to the reaction vessel with a vacuum degree ≤ -0.09MPa for 6 hours. The organic solvents volatilized or generated during the reaction are collected using a special solvent recovery device to obtain a component B solution with a concentration of 80wt%.

[0080]

[0081] Chemical structure of component B 1

[0082] Preparation Example 4

[0083] This preparation example provides a component B solution, the preparation method of which includes the following steps:

[0084] S1. Dissolve 1434g of 4-phenylacetylene phthalic anhydride and 1699g of 2,3,3',4'-biphenyltetraic dianhydride monomer in 4699g of ethanol, and reflux at 78℃ for 3h to obtain an esterification solution with a concentration of 40wt%.

[0085] S2. Dissolve 925g TFMBZ and 943g diaminophenylcarboroline diamine monomer in 4357g ethanol solvent, and heat to 45℃ under inert gas protection to obtain a diamine solution with a concentration of 30wt%.

[0086] S3. Pour the esterification solution obtained above into the diamine solution, and heat it to 70°C for 3 hours under stirring in the reaction vessel; further heat it to 100°C, and at the same time apply a continuous vacuum to the reaction vessel with a vacuum degree ≤ -0.09MPa for 4 hours. The organic solvents volatilized or generated during the reaction are collected using a special solvent recovery device to obtain a B component solution with a concentration of 80wt%.

[0087]

[0088] Chemical structure of component B 2

[0089] Preparation Example 5

[0090] This preparation example provides a component B solution, the preparation method of which includes the following steps:

[0091] S1. Dissolve 1884g of 4-PEPA and 1117g of 2,3,3',4'-biphenyltetraic dianhydride monomer in 4699g of ethanol and reflux at 78°C for 4h to obtain an esterification solution with a concentration of 40wt%.

[0092] S2. Dissolve 925g of 3,4-ODA and 943g of diaminophenylcarboroline diamine monomer in 4357g of ethanol solvent, and heat to 55℃ under inert gas protection to obtain a diamine solution with a concentration of 30wt%.

[0093] S3. Pour the esterification solution obtained above into the diamine solution, and heat it to 78°C for 4 hours under stirring in the reaction vessel; further heat it to 95°C, and at the same time apply a continuous vacuum to the reaction vessel with a vacuum degree ≤ -0.09MPa for 6 hours. The organic solvents volatilized or generated during the reaction are collected using a special solvent recovery device to obtain a B component solution with a concentration of 80wt%.

[0094]

[0095] Chemical structure of component B 3

[0096] Example 1

[0097] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0098] S1. The resin solution of component B obtained in Preparation Example 3 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 20% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 4000 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 250°C and reacted under vacuum for 6 hours. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0099] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0100] Example 2

[0101] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0102] S1. The resin solution of component B obtained in Preparation Example 3 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 40% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 250°C and reacted under vacuum for 6 hours. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0103] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0104] Example 3

[0105] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0106] S1. The resin solution of component B obtained in Preparation Example 3 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 60% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 250°C and reacted under vacuum for 6 hours. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0107] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0108] Example 4

[0109] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0110] S1. The resin solution of component B obtained in Preparation Example 3 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 80% of the total content of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 250°C and reacted under vacuum for 6 hours. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0111] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0112] The powdered carborane hybrid RTM polyimide resins obtained in Examples 1-4 were subjected to performance tests, and the results are shown in Table 1.

[0113] Table 1 Properties of RTM-1 Resin

[0114]

[0115] Example 5

[0116] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0117] S1. The resin solution of component B obtained in Preparation Example 4 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 20% of the total content of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 210°C and reacted under vacuum for 6 hours. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0118] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0119] Example 6

[0120] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0121] S1. The resin solution of component B obtained in Preparation Example 4 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 40% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 210°C and reacted under vacuum for 6 hours. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0122] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0123] Example 7

[0124] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0125] S1. The resin solution of component B obtained in Preparation Example 4 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 60% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 210°C and reacted under vacuum for 6 hours. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0126] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0127] Example 8

[0128] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0129] S1. The resin solution of component B obtained in Preparation Example 4 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it, controlling the content of component A to be 80% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device, controlling the stirring speed to be 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 210°C and reacted under vacuum for 6 hours. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0130] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0131] The powdered carborane hybrid RTM polyimide resins obtained in Examples 5-8 were subjected to performance tests, and the results are shown in Table 2.

[0132] Table 2 Properties of RTM-1 Resin

[0133]

[0134] Example 9

[0135] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0136] S1. The resin solution of component B obtained in Preparation Example 5 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 20% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 220°C and reacted under vacuum for 5 h. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0137] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0138] Example 10

[0139] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0140] S1. The resin solution of component B obtained in Preparation Example 5 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 40% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 220°C and reacted under vacuum for 5 h. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0141] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0142] Example 11

[0143] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0144] S1. The resin solution of component B obtained in Preparation Example 5 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it. The content of component A was controlled to be 60% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device at a stirring speed of 3500 r / min. Then, it was subjected to ultrasonic vibration. Next, the mixture was heated to 220°C and reacted under vacuum for 5 h. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0145] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0146] Example 12

[0147] This embodiment provides a carborane hybrid RTM polyimide resin, the preparation method of which includes the following steps:

[0148] S1. The resin solution of component B obtained in Preparation Example 5 was heated to 100°C, and the resin powder of component A obtained in Preparation Example 2 was added to it, controlling the content of component A to be 80% of the total of component A and component B. First, the mixture was stirred using a high-speed stirring device, controlling the stirring speed to be 3500 r / min, and then ultrasonically vibrated. Next, the mixture was heated to 220°C and reacted under vacuum for 5 h. After cooling, blocky carborane hybrid RTM polyimide resins with different amounts of component A were obtained.

[0149] S2. The block resin obtained in step S1 is mechanically pulverized to control the particle size of the pulverized resin to 50 mesh, thereby obtaining powdered carborane hybrid RTM polyimide resin.

[0150] The performance of the powdered carborane hybrid RTM polyimide resins obtained in Examples 9-12 was tested, and the results are shown in Table 3.

[0151] Table 3 Properties of RTM-3 Resin

[0152]

[0153] As can be seen from the above embodiments, the present invention can achieve low viscosity and long open period while ensuring high resistance by adjusting the concentrations of component A and component B, adjusting the resin viscosity and open period by component A, and adjusting the resin strength and heat resistance by component B.

[0154] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A carborane hybrid RTM polyimide resin, characterized in that, The carborane hybrid RTM polyimide resin comprises component A and component B; the content of component A accounts for 10% to 90% of the total content of component A and component B. Component A has the structure shown in Formula I: Formula I; Component B has the structure shown in Formula II: Formula II In Formula II, X1 represents any of the following substituents: 、 、 ； n is 1; The carborane-hybridized RTM polyimide resin is obtained through the following preparation process: S2.1 Dissolve 4-phenylacetylene phthalic anhydride and 2,3,3',4'-biphenyltetraic dianhydride monomers in an alcohol solvent and react to obtain an esterified solution; S2.2 Dissolve the diamine monomer and carborane diamine monomer in an organic solvent, and heat under an inert gas to obtain a mixed diamine solution; S2.3 The esterification solution is poured into the mixed diamine solution, and a polymerization reaction is carried out to obtain reactant 1; S1. Heat the reactant 1 to a first temperature, add component A, stir, then sonicate, then heat to a second temperature, perform a vacuum reaction, and then cool to obtain a blocky carborane hybrid RTM polyimide resin. S2. The blocky carborane hybrid RTM polyimide resin is pulverized to obtain powdered carborane hybrid RTM polyimide resin.

2. The carborane hybrid RTM polyimide resin according to claim 1, characterized in that, The preparation method of component A is as follows: S1.1 Dissolve 4-phenylacetylene phthalic anhydride in an alcohol solvent and react to obtain an esterified solution; S1.2 Dissolve the carborane diamine monomer in an organic solvent and heat under inert gas protection to obtain a diamine solution; S1.3 The esterification solution and the diamine solution are mixed to carry out a polymerization reaction to obtain a resin solution; S1.4 The resin solution is heated and reacted under vacuum, and then cooled to obtain a block resin containing a compound with the structure shown in Formula I. The block resin described in S1.5 is pulverized to obtain component A; Component A is a resin powder with a particle size of 50-200 mesh.

3. The carborane hybrid RTM polyimide resin according to claim 2, characterized in that, In step S1.1, the reaction temperature is 60℃-90℃, the reaction time is 1h-4h, and the concentration of the esterification solution obtained is 20wt%-80wt%. In step S1.2, the heating temperature is 40℃-80℃, and the concentration of the diamine solution obtained after heating is 20wt%-80wt%. In step S1.3, the polymerization reaction includes: pouring the esterification solution into the diamine solution, and heating the solution to 60℃-80℃ under stirring for 1h-5h for polymerization reaction; Then the temperature is raised to 80-120℃, the vacuum degree is controlled to be ≤-0.09MPa, and the reaction is carried out for 1h-12h to obtain the resin solution; In step S1.4, the temperature for heating is 150℃-260℃, and the reaction time under vacuum is 1h-6h.

4. The carborane hybrid RTM polyimide resin according to claim 1, characterized in that, In step S2.1, the reaction temperature is 60℃-90℃, the reaction time is 1h-6h, and the concentration of the obtained esterification solution is 20wt%-80wt%. In step S2.2, the heating temperature is 40℃-60℃, and the concentration of the mixed diamine solution obtained by heating is 20wt%-80wt%. In step S2.3, the polymerization reaction includes: pouring the esterification solution into the mixed diamine solution, and heating to 60℃-80℃ under stirring for 1h-5h for polymerization reaction; Reheat to 80-120℃, maintain a vacuum of ≤-0.09MPa, and react for 1-12 hours.

5. The carborane hybrid RTM polyimide resin according to claim 1, characterized in that, The first temperature is 90-120℃, and the second temperature is 150℃-260℃; In step S1, the reaction time of the vacuum reaction is 1h-6h; In step S2, the particle size of the powdered carborane hybrid RTM polyimide resin is ≥20 mesh.

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