Preparation and application of carborane modified polyphenyl quinoxaline
By introducing carboalkyl groups into polyphenylquinoxoline materials, the carboane modified polyphenylquinoxolines is solved, and the material has insufficient heat resistance in high temperature environments is achieved, and it has achieved higher thermal stability and heat resistance. It is suitable for aerospace and other fields.
Patent Information
- Application Number
- CN202510482046.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-17
- Publication Date
- 2025-08-19
AI Technical Summary
The existing polyphenylquinoline materials have insufficient heat resistance in high temperature environments, making it difficult to meet the application needs in aerospace and other fields.
Carboroalkyl groups are introduced into the polymer backbone, and the carboroane modified polyphenylquinoline is formed by covalent bonding, improving the thermal stability and heat resistance of the material.
It significantly improves the thermal stability and heat resistance of the material, making it show excellent performance in high temperature environments, and is suitable for aerospace and other fields.
Smart Images
Figure CN120504686A_ABST
Abstract
Description
Technical Field
[0001] The present application belongs to the technical field of polymer materials, and in particular relates to the preparation and application of a carborane-modified polyphenylquinoxaline with excellent thermal stability. Background Art
[0002] Heat-resistant materials (high-temperature materials) have important applications in aerospace, energy, chemical industry, electronics, etc. With the rapid development of defense industry, electronic information industry, aerospace and other fields, the demand for high-performance high-temperature resistant materials continues to increase.
[0003] Poly(phenylquinoxaline, PPQ) is a high-performance aromatic heterocyclic polymer, and its thermal properties are the core advantage of its application in high-temperature environments. In the molecular structure of PPQ, the phenyl-substituted quinoxaline ring has high rigidity and conjugation properties, which endow the material with excellent thermal stability. The thermal decomposition temperature of PPQ in a nitrogen environment is usually over 500°C, and it can be used stably for a long time below 300°C without obvious performance degradation. It is suitable for high-temperature electronic devices and aviation materials. In recent years, with the widespread application of polyphenylquinoxaline in the field of high-temperature resistance, higher requirements have been placed on the thermal properties of PPQ. Therefore, the study of the heat resistance of polyphenylquinoxaline is of great practical significance.
[0004] In the field of polymer materials, the introduction of boron-carbon cluster structural units has become an effective molecular design strategy to improve heat resistance. When carborane groups are embedded in the polymer backbone through covalent bonds, the thermal properties of the polymer can be significantly improved. This is because carborane is a cage-like cluster composed of carbon, boron and hydrogen. Its unique closed structure has high symmetry and electronic delocalization, forming a stable three-dimensional aromatic system. This structure makes it difficult to decompose at high temperatures, which directly improves the overall heat resistance of the composite material. Secondly, when carborane is dispersed in the polymer matrix, its rigid cage structure can physically hinder the movement of polymer chain segments and improve the thermal stability of the material. This structural characteristic makes it show important application potential in the development of high-temperature resistant materials.
[0005] Based on the above reasons, in order to obtain a polymer material with better heat resistance, the present invention designs and develops a carborane tetraamine monomer and a carborane-modified polyphenylquinoxaline compound, and describes its preparation method and application as a heat-resistant material. Summary of the Invention
[0006] The present invention studies the preparation and application of carborane-modified polyphenylquinoxalines and develops a class of tetraamine monomers containing carborane groups. These monomers can be copolymerized with different types of monomers containing didione and other tetraamine monomers to form new carborane-modified polyphenylquinoxalines, which are expected to be used as high-temperature resistant materials in aviation, aerospace and other fields.
[0007] The present invention first provides a compound containing a carborane tetraamine monomer:
[0008]
[0009]
[0010] The present invention provides a method for preparing a carborane-containing tetraamine monomer, comprising the following steps:
[0011] Under the action of a base and a palladium catalyst, compound A and compound B undergo a coupling reaction to obtain the compound;
[0012] R1 is selected from
[0013]
[0014] R1 is selected from
[0015] R2 is selected from
[0016] In the method, the palladium catalyst is selected from at least one of DPPFPdCl2, PdCl2(PPh3)2, Pd(PPh3)4, Pd(OAc)2, and Pd2(dba)3.
[0017] The base is selected from at least one of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, sodium hydroxide, and potassium hydroxide.
[0018] The solvent is selected from at least one of dichloromethane, chloroform, 1,4-dioxane, tetrahydrofuran, acetonitrile, methanol, N,N-dimethylformamide, and N,N-dimethylacetamide.
[0019] A polymer having a structure as shown in Formula V,
[0020]
[0021] Wherein, Ar1 is selected from
[0022] R3 is selected from -H, -CF3.
[0023] X is selected from a single bond, -CH2-, -O-, -S-, -SO2-, and -C(CF3)2-.
[0024] The molar ratio of y:x is not greater than 1:1 and is not zero.
[0025] Preferably, the molar ratio of y:x is 1:1-100.
[0026] Preferably, the molar ratio of y:x is 1:1-20.
[0027] Preferably, the molar ratio of y:x is 1:1-10.
[0028] The preparation method of the polymer comprises the following steps:
[0029] At least one of the carborane tetraamine monomers, at least one of the compounds represented by formula VI, and at least one of the compounds represented by formula VII are subjected to a polymerization reaction in a solvent to obtain a compound represented by formula V.
[0030]
[0031] Wherein, X is a single bond, -CH2-, -O-, -S-, -SO2-, or -C(CF3)2-.
[0032] Ar1 is
[0033] R3 is -H or -CF3.
[0034] The method, wherein the reaction solvent is selected from at least one of N-methylpyrrolidone, m-cresol, p-chlorophenol, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide;
[0035] The reaction temperature is 100-150°C;
[0036] The reaction time is 24-48h.
[0037] The invention relates to an application of the compound in the preparation of polyphenylquinoxaline.
[0038] The application of the polyphenylquinoxaline in the preparation of high-temperature resistant materials.
[0039] The present invention also includes films, resins, and coatings prepared from the carborane-modified polyphenylquinoxaline compound of Formula V, as well as the use of the carborane-modified polyphenylquinoxaline compound of Formula V or the film, resin, and coating prepared from the carborane-modified polyphenylquinoxaline compound of Formula V as a high-temperature proton exchange membrane for fuel cells in aqueous solution, and the use of the film prepared from the carborane-modified polyphenylquinoxaline compound of Formula V in the preparation of heat-resistant films. The aqueous solution is specifically an acidic, alkaline, or neutral solution.
[0040] This application discloses a method for synthesizing a tetraamine monomer containing a carborane structure, as well as a method for preparing carborane-modified polyphenylquinoxaline. This material, based on a polyphenylquinoxaline backbone and copolymerized with a polyhedral caged carborane, produces a series of derivatives exhibiting excellent heat resistance. Due to their remarkable heat resistance, these materials are expected to have applications in, but not limited to, heat-resistant materials, aviation, and aerospace. BRIEF DESCRIPTION OF THE DRAWINGS
[0041] The drawings are only for the purpose of illustrating specific embodiments and are not to be considered limiting of the present application.
[0042] Figure 1 is the H NMR spectrum of Example 5;
[0043] Figure 2 is the infrared image of Example 61;
[0044] Figure 3 This is the TGA curve of Example 62. DETAILED DESCRIPTION
[0045] The following non-limiting examples may enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way. Any person skilled in the art who is familiar with the present invention may, within the technical scope disclosed herein, make equivalent replacements or changes according to the technical solutions and inventive concepts of the present invention, all of which fall within the scope of protection of the present invention. The methods for structural and performance testing of the resulting product compounds or polymers in the following examples are all conventional testing methods unless otherwise specified. The molecular weight of the polymers obtained in the examples is determined by GPC, and the obtained molecular weight is the number average molecular weight.
[0046] Thermogravimetric analysis (TGA): The prepared borane-modified polyphenylquinoxaline was tested using a thermogravimetric analyzer (TA Instruments, USA, Q500 series) at a heating rate of 10°C / min.
[0047] Example 1, synthesis of compound of formula I:
[0048]
[0049] The reaction system was evacuated and replaced with argon three times. Maintaining the argon atmosphere, a 500-ml Schereck flask was charged with 4.4 mmol of 1,2-bis(4-bromophenyl)-carborane, 22.02 mmol of 3,4-diaminophenylboronic acid pinacol ester, and 22.02 mmol of potassium carbonate. The mixture was dissolved in THF / H₂O (5 / 1, 20 ml). The mixture was heated to 85°C in an oil bath and stirred for 5 minutes. Then, 440.33 μmol of DPPFPdCl₂ was added. The reaction was continued at 85°C for 10 hours, monitored by TLC. After completion, the reaction was cooled to room temperature. 500 ml of DCM and 500 mL of saturated sodium chloride were added to the flask. The filtrate was extracted with DCM. The product dissolved in the DCM layer. The solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography to obtain a white product in a 73% yield. The eluent was petroleum ether:ethyl acetate = 5:1 (v:v).
[0050] The structural detection data of the compound are shown below:
[0051] 1 H NMR (400MHz, DMSO-d6): δ7.39(dd,J=59.5,7.9Hz,4H), δ6.73(s,1H), δ6.64(d,J=7.6Hz, 1H), δ6.47(d,J=7.8Hz,1H), δ4.68(s,2H), δ4.48(s,2H).
[0052] From the above data, it can be seen that the structure of formula I is correct.
[0053] Example 2, synthesis of compound of formula II:
[0054]
[0055] The reaction system was evacuated and replaced with argon three times. Maintaining the argon atmosphere, a 500-ml Schereck flask was charged with 4.4 mmol of 1,2-bis(4-bromophenyl)-carborane, 22.02 mmol of 2,3-diaminophenylboronic acid pinacol ester, and 22.02 mmol of potassium carbonate. The mixture was dissolved in THF / H₂O (5 / 1, 20 ml). The mixture was heated to 85°C in an oil bath and stirred for 5 minutes. Then, 440.33 μmol of DPPFPdCl₂ was added. The reaction was continued at 85°C for 10 hours and monitored by TLC. After completion, the reaction was cooled to room temperature. 500 ml of DCM and 500 mL of saturated sodium chloride were added to the flask. The filtrate was extracted with DCM. The product dissolved in the DCM layer. The solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography in a 70% yield. The eluent was petroleum ether:ethyl acetate = 5:1 (v:v).
[0056] Example 3, synthesis of compound of formula III:
[0057]
[0058] The reaction system was evacuated and replaced with argon three times. Maintaining the argon atmosphere, a 500-ml Schereck flask was charged with 4.4 mmol of 1,2-bis(3-bromophenyl)-carborane, 22.02 mmol of 3,4-diaminophenylboronic acid pinacol ester, and 22.02 mmol of potassium carbonate. The mixture was dissolved in THF / H₂O (5 / 1, 20 ml). The mixture was heated to 85°C in an oil bath and stirred for 5 minutes. Then, 440.33 μmol of DPPFPdCl₂ was added. The reaction was continued at 85°C for 10 hours and monitored by TLC. After completion, the reaction was cooled to room temperature. 500 ml of DCM and 500 mL of saturated sodium chloride were added to the flask. The filtrate was extracted with DCM. The product dissolved in the DCM layer. The solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography to obtain a white product in a 73% yield. The eluent was petroleum ether:ethyl acetate = 5:1 (v:v).
[0059] Example 4, synthesis of compound of formula IV:
[0060]
[0061] The reaction system was evacuated and replaced with argon three times. Maintaining the argon atmosphere, a 500-ml Schereck flask was charged with 4.4 mmol of 1,2-bis(3-bromophenyl)-carborane, 22.02 mmol of 2,3-diaminophenylboronic acid pinacol ester, and 22.02 mmol of potassium carbonate. The mixture was dissolved in THF / H₂O (5 / 1, 20 ml). The mixture was heated to 85°C in an oil bath and stirred for 5 minutes. Then, 440.33 μmol of DPPFPdCl₂ was added. The reaction was continued at 85°C for 10 hours and monitored by TLC. After completion, the reaction was cooled to room temperature. 500 ml of DCM and 500 mL of saturated sodium chloride were added to the flask. The filtrate was extracted with DCM. The product dissolved in the DCM layer. The solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography to obtain a white product in a 72% yield. The eluent was petroleum ether:ethyl acetate = 5:1 (v:v).
[0062] Example 5, Synthesis of Compound P1:
[0063]
[0064] A Schereck flask equipped with a magnetic stirrer was evacuated and replaced with argon three times, maintaining an argon atmosphere in the reaction system. Compound VI was added and dissolved in m-cresol. Stirring was continued at room temperature for 10 minutes until compound VI was completely dissolved, resulting in a uniform yellow-brown solution. Compound VII was then added, and m-cresol was added until the solids content of the reaction system reached approximately 20%. Compound I was then added to the reaction flask under argon, and the reaction was continued at 120°C for 12 hours. After the reaction, the mixture was cooled to room temperature and then poured into anhydrous methanol to precipitate a yellow solid. The solid was chopped and stirred in anhydrous methanol overnight to completely remove the m-cresol. The mixture was filtered through a Büchner funnel, washed repeatedly with anhydrous methanol, and then dried thoroughly in a vacuum drying oven. Compound VI, compound VII, and compound I were added in the ratio of 2.33 mmol, 2.33 mmol, and 0 mmol, respectively, to obtain a yellow solid product, designated P1-0. The mole fraction of the carborane tetraamine monomer was 0 mol%. The compound of formula VI, the compound of formula VII, and the compound of formula I were added in the order of 3.93 mmol, 4.91 mmol, and 982.96 μmol, to obtain a yellow solid strip product, designated as P1-1. The molar fraction of the carborane tetraamine monomer was 10 mol%. The compound of formula VI, the compound of formula VII, and the compound of formula I were added in the order of 2.95 mmol, 3.93 mmol, and 982.96 μmol, to obtain a yellow solid strip product, designated as P1-2. The molar fraction of the carborane tetraamine monomer was 13 mol%. The compound of formula VI, the compound of formula VII, and the compound of formula I were added in the order of 1.97 mmol, 2.95 mmol, and 982.96 μmol, to obtain a yellow solid strip product, designated as P1-3. The molar fraction of the carborane tetraamine monomer was 17 mol%.
[0065] The H NMR spectra of compounds P1-0, P1-1, P1-2 and P1-3 are shown in Figure 2. Figure 1 shown.
[0066] Molecular weight (g / mol): P1-0: 23640; P1-1: 27419; P1-2: 31269; P1-3: 33597.
[0067] Example 6, Synthesis of Compound P2:
[0068]
[0069] A Schereck flask equipped with a magnetic stirrer was evacuated and replaced with argon three times, maintaining an argon atmosphere in the reaction system. 1.97 mmol of compound VI was added and dissolved in m-cresol. Stirring was continued at room temperature for 10 minutes until compound VI was completely dissolved, resulting in a uniform yellow-brown solution. 2.95 mmol of compound VII was then added, and m-cresol was added until the solid content of the reaction system reached approximately 20%. Next, under argon, 982.96 μmol of compound I was added to the reaction flask and reacted at 120°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and then poured into anhydrous methanol to precipitate a solid. The solid was chopped and stirred in anhydrous methanol overnight to completely remove the m-cresol. The mixture was filtered through a Buchner funnel, washed repeatedly with anhydrous methanol, and then dried thoroughly in a vacuum drying oven to obtain the product, designated P2.
[0070] Example 7, Synthesis of Compound P3:
[0071]
[0072] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P3.
[0073] Example 8, Synthesis of Compound P4:
[0074]
[0075] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P4.
[0076] Example 9, Synthesis of Compound P5:
[0077]
[0078] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P5.
[0079] Example 10, Synthesis of Compound P6:
[0080]
[0081] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P6.
[0082] Example 11, Synthesis of Compound P7:
[0083]
[0084] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P7.
[0085] Example 12, Synthesis of Compound P8:
[0086]
[0087] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P8.
[0088] Example 13, Synthesis of Compound P9:
[0089]
[0090] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P9.
[0091] Example 14, Synthesis of Compound P10:
[0092]
[0093] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P10.
[0094] Example 15, Synthesis of Compound P11:
[0095]
[0096] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P11.
[0097] Example 16, Synthesis of Compound P12:
[0098]
[0099] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P12.
[0100] Example 17, Synthesis of Compound P13:
[0101]
[0102] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P13.
[0103] Example 18, Synthesis of Compound P14:
[0104]
[0105] The synthesis method was similar to that of Example 6 to obtain carborane-modified polyphenylquinoxaline, which was designated as P14.
[0106] Example 19, Synthesis of Compound P15:
[0107]
[0108] A Schereck flask equipped with a magnetic stirrer was evacuated and replaced with argon three times, maintaining an argon atmosphere in the reaction system. 1.97 mmol of the compound of formula VI was added and dissolved in m-cresol. The mixture was stirred at room temperature for 10 minutes until the compound of formula VI was completely dissolved to form a uniform yellow-brown solution. 2.95 mmol of the compound of formula VII was then added, and m-cresol was added until the solid content of the reaction system reached approximately 20%. Then, under argon, 982.96 μmol of the compound of formula II was added to the reaction flask and reacted at 120°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and then poured into anhydrous methanol to precipitate a solid. The solid was chopped and placed in anhydrous methanol and stirred overnight to completely remove the m-cresol. The mixture was filtered through a Buchner funnel and repeatedly washed with anhydrous methanol. It was then dried in a vacuum drying oven to obtain the product, designated P15.
[0109] Example 20, Synthesis of Compound P16:
[0110]
[0111] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P16.
[0112] Example 21, Synthesis of Compound P17:
[0113]
[0114] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P17.
[0115] Example 22, Synthesis of Compound P18:
[0116]
[0117] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P18.
[0118] Example 23, Synthesis of Compound P19:
[0119]
[0120] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P19.
[0121] Example 24, Synthesis of Compound P20:
[0122]
[0123] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P20.
[0124] Example 25, Synthesis of Compound P21:
[0125]
[0126] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P21.
[0127] Example 26, Synthesis of Compound P22:
[0128]
[0129] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P22.
[0130] Example 27, Synthesis of Compound P23:
[0131]
[0132] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P23.
[0133] Example 28, Synthesis of Compound P24:
[0134]
[0135] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P24.
[0136] Example 29, Synthesis of Compound P25:
[0137]
[0138] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P25.
[0139] Example 30, Synthesis of Compound P26:
[0140]
[0141] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P26.
[0142] Example 31, Synthesis of Compound P27:
[0143]
[0144] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P27.
[0145] Example 32, Synthesis of Compound P28:
[0146]
[0147] The synthesis method was similar to that of Example 19 to obtain carborane-modified polyphenylquinoxaline, which was designated as P28.
[0148] Example 33, Synthesis of Compound P29:
[0149]
[0150] A Schereck flask equipped with a magnetic stirrer was evacuated and replaced with argon three times, maintaining an argon atmosphere in the reaction system. 1.97 mmol of the compound of formula VI was added and dissolved in m-cresol. The mixture was stirred at room temperature for 10 minutes until the compound of formula VI was completely dissolved, resulting in a uniform yellow-brown solution. 2.95 mmol of the compound of formula VII was then added, and m-cresol was added until the solid content of the reaction system reached approximately 20%. Then, under argon, 982.96 μmol of the compound of formula III was added to the reaction flask and reacted at 120°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and then poured into anhydrous methanol to precipitate a solid. The solid was chopped and placed in anhydrous methanol and stirred overnight to completely remove the m-cresol. The mixture was filtered through a Buchner funnel, washed repeatedly with anhydrous methanol, and then dried thoroughly in a vacuum drying oven to obtain the product, designated P29.
[0151] Example 34, Synthesis of Compound P30:
[0152]
[0153] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P30.
[0154] Example 35, Synthesis of Compound P31:
[0155]
[0156] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P31.
[0157] Example 36, Synthesis of Compound P32:
[0158]
[0159] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P32.
[0160] Example 37, Synthesis of Compound P33:
[0161]
[0162] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P33.
[0163] Example 38, Synthesis of Compound P34:
[0164]
[0165] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P34.
[0166] Example 39, Synthesis of Compound P35:
[0167]
[0168] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P35.
[0169] Example 40, Synthesis of Compound P36:
[0170]
[0171] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P36.
[0172] Example 41, Synthesis of Compound P37:
[0173]
[0174] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P37.
[0175] Example 42, Synthesis of Compound P38:
[0176]
[0177] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P38.
[0178] Example 43, Synthesis of Compound P39:
[0179]
[0180] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P39.
[0181] Example 44, Synthesis of Compound P40:
[0182]
[0183] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P40.
[0184] Example 45, Synthesis of Compound P41:
[0185]
[0186] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P41.
[0187] Example 46, Synthesis of Compound P42:
[0188]
[0189] The synthesis method was similar to that of Example 33 to obtain carborane-modified polyphenylquinoxaline, which was designated as P42.
[0190] Example 47, Synthesis of Compound P43:
[0191]
[0192] A Schereck flask equipped with a magnetic stirrer was evacuated and replaced with argon three times, maintaining an argon atmosphere in the reaction system. 1.97 mmol of the compound of formula VI was added and dissolved in m-cresol. The mixture was stirred at room temperature for 10 minutes until the compound of formula VI was completely dissolved, resulting in a uniform yellow-brown solution. 2.95 mmol of the compound of formula VII was then added, and m-cresol was added until the solid content of the reaction system reached approximately 20%. Next, under argon, 982.96 μmol of the compound of formula IV was added to the reaction flask, and the reaction was carried out at 120°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and then poured into anhydrous methanol to precipitate a solid. The solid was chopped and placed in anhydrous methanol and stirred overnight to completely remove the m-cresol. The mixture was filtered through a Buchner funnel, washed repeatedly with anhydrous methanol, and then dried thoroughly in a vacuum drying oven to obtain the product, designated P43.
[0193] The following Example 48, the synthesis of compound P44:
[0194]
[0195] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P44.
[0196] Example 49, Synthesis of Compound P45:
[0197]
[0198] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P45.
[0199] Example 50, Synthesis of Compound P46:
[0200]
[0201] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P46.
[0202] Example 51, Synthesis of Compound P47:
[0203]
[0204] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P47.
[0205] Example 52, Synthesis of Compound P48:
[0206]
[0207] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P48.
[0208] Example 53, Synthesis of Compound P49:
[0209]
[0210] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P49.
[0211] Example 54, Synthesis of Compound P50:
[0212]
[0213] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P50.
[0214] Example 55, Synthesis of Compound P51:
[0215]
[0216] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P51.
[0217] Example 56, Synthesis of Compound P52:
[0218]
[0219] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P52.
[0220] Example 57, Synthesis of Compound P53:
[0221]
[0222] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P53.
[0223] Example 58, Synthesis of Compound P54:
[0224]
[0225] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P54.
[0226] Example 59, Synthesis of Compound P55:
[0227]
[0228] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P55.
[0229] Example 60, Synthesis of Compound P56:
[0230]
[0231] The synthesis method was similar to that of Example 47 to obtain carborane-modified polyphenylquinoxaline, which was designated as P56.
[0232] Example 61, infrared test of compounds P1-0, P1-1, P1-2, and P1-3 prepared in Example 5:
[0233] Compounds P1-0, P1-1, P1-2, and P1-3 were tested using a Nicoleti N10 micro-infrared spectrometer with a wavenumber range of 4000 cm -1 ~500cm -1 .
[0234] The infrared spectra of compounds P1-0, P1-1, P1-2 and P1-3 are as follows: Figure 2 shown.
[0235] Example 62, thermogravimetric test of compounds P1-0, P1-1, P1-2, and P1-3:
[0236] Compounds P1-0, P1-1, P1-2, and P1-3 were tested using a TA Instruments Q500 thermogravimetric analyzer with a heating rate of 10°C / min, a nitrogen flow rate of 50 mL / min, and a temperature range of 25 to 900°C. The thermal decomposition properties of the polymers were tested, and the thermal decomposition temperature T d5％ 、T d10％ 、T d30％and the residual carbon rate C at 900℃ y900℃ The TGA curves of compounds P1-0, P1-1, P1-2, and P1-3 are shown in Figure 2. Figure 3 The key thermal data of compounds P1-0, P1-1, P1-2, and P1-3 are shown in Table 1.
[0237] Table 1 Key thermal data of compounds P1-0, P1-1, P1-2, and P1-3
[0238] <![CDATA[T d5％ / ℃]]> <![CDATA[T d10％ / ℃]]> <![CDATA[T d30％ / ℃]]> <![CDATA[C y900℃ / %]]> P1-0 509 522 546 54.15 P1-1 514 529 649 65.65 P1-2 528 544 857 69.53 P1-3 535 573 >900 78.65
[0239] It can be seen from the above experimental data that with the increase of the amount of carborane tetraamine monomer, the thermal properties of the polymer are significantly improved.
Claims
1. A carborane tetraamine monomer, characterized in that The structures are shown in formulas I, II, III, and IV.
2. The method for preparing the compound according to claim 1, characterized in that: The steps include: Under the action of a base and a palladium catalyst, compound A and compound B undergo a coupling reaction to obtain the compound; R1 is selected from R2 is selected from 3. The method according to claim 2, wherein: The palladium catalyst is selected from at least one of DPPFPdCl2, PdCl2(PPh3)2, Pd(PPh3)4, Pd(OAc)2, and Pd2(dba)3; The base is selected from at least one of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, sodium hydroxide, and potassium hydroxide. The solvent is selected from at least one of dichloromethane, chloroform, 1,4-dioxane, tetrahydrofuran, acetonitrile, methanol, N,N-dimethylformamide, and N,N-dimethylacetamide.
4. A polymer, characterized in that The structure is shown in Formula V, Wherein, Ar1 is selected from R3 is selected from -H, -CF3; X is selected from a single bond, -CH2-, -O-, -S-, -SO2-, and -C(CF3)2-. The molar ratio of y:x is not greater than 1:1 and is not zero.
5. A polymer according to claim 4, characterized in that The molar ratio of y:x is 1:1-20.
6. A polymer according to claim 4, characterized in that The molar ratio of y:x is 1:1-10.
7. A method for preparing the compound according to claim 4, characterized in that: The steps include: At least one of the carborane tetraamine monomers according to claim 1, at least one of the compounds represented by formula VI, and at least one of the compounds represented by formula VII are reacted in a solvent to obtain a compound represented by formula V through polymerization; Wherein, X is a single bond, -CH2-, -O-, -S-, -SO2-, -C(CF3)2-; Ar1 is R3 is -H or -CF3.
8. The method according to claim 7, wherein: The reaction solvent is selected from at least one of N-methylpyrrolidone, m-cresol, p-chlorophenol, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; The reaction temperature is 100-150°C; The reaction time is 24-48h.
9. Use of the compound according to claim 1 in the preparation of polyphenylquinoxaline.
10. Use of the polyphenylquinoxaline according to claim 4 in the preparation of high temperature resistant materials.