Silicon-hydrogen-terminated silicon-containing aryne resin as well as preparation method and application thereof

Abstract

The invention relates to a silicon-hydrogen-terminated silicon-containing aryne resin and a preparation method and application thereof, the structural formula of the silicon-hydrogen-terminated silicon-containing aryne resin is as follows: in the formula, R1 and R2 are respectively and independently CH3, CH2 = CH, H or phenyl; n is equal to 1-9. The preparation method comprises the following steps: firstly, carrying out Grignard reaction on 1, 3-diacetylene benzene and a Grignard reagent to obtain a compound 1 as shown in a formula I; carrying out polymerization reaction on the compound 1 and a compound 2 as shown in a formula II to obtain a compound 3 as shown in a formula III; and then carrying out reduction reaction on the compound 3 and lithium aluminum hydride to obtain the silicon-hydrogen-terminated silicon-containing aryne resin. Compared with the prior art, the silicon-hydrogen-terminated silicon-containing aryne resin prepared by the invention has excellent heat resistance, has extremely high thermal decomposition temperature of 5% of cured substance weight loss in nitrogen and air, has excellent processability and has an extremely wide processable temperature window.

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis technology, and relates to a silane-containing aromatic resin with silane end capping, its preparation method and application. Background Technology

[0002] Silica-containing aromatic yne resin (PSA) is a high-performance thermosetting resin that has attracted widespread attention due to its excellent thermal stability, outstanding dielectric properties, and ceramizability. The properties of a polymer mainly depend on its molecular structure, with end groups playing a crucial role in the synthesis and modification of the resin. The structural characteristics of the molecular chain end groups directly affect the resin's thermal stability, toughness, mechanical properties, interfacial adhesion, and corrosion resistance.

[0003] Currently, most common PSA resins use -C≡CH as the end group. Due to the heterogeneous nature of the reaction process, the molecular weight is often difficult to precisely control. The hydrogen atom on the terminal alkyne group has a certain acidity (pKa value of about 25) and can react with a variety of nucleophiles and electrophiles, such as Sonogashira coupling, carbon metallization of alkynes, hydrogenation, polymerization, and cyclotrimerization. During the polymerization of PSA resin, the terminal alkyne hydrogen helps to form a stable cross-linking network, but it may also become the initiation point for thermal degradation, thus affecting the high-temperature antioxidant properties of the cured resin. For example, Liu et al. (Polym. Eng. Sci. 2022, 62 (3): 793-801) synthesized silicic aromatic yne resins with different side group end groups of -C≡CH. The 5% decomposition temperature of the dimethyl silicic aromatic yne resin in air was 527 °C, and the mass retention rate at 800 °C was 26.7%.

[0004] Furthermore, the terminal -C≡CH can interact with the active sites of various metal-based catalysts (such as Karstedt catalysts), leading to catalyst poisoning and deactivation, which is detrimental to its blending modification with other resins. Therefore, to reduce the adverse effects of the terminal -C≡CH on PSA resin, while increasing the silicon content of the resin and enhancing its high-temperature oxidation resistance, this invention replaces the terminal group of PSA resin with a Si-H group. Summary of the Invention

[0005] The purpose of this invention is to provide a silane-hydrogen-terminated silane-arylene resin, its preparation method, and its applications, addressing the problems of existing silane-arylene resins, such as the poisoning of metal-based catalysts due to terminal acetylation hydrogens, a narrow processing temperature window, and low silicon content hindering ceramization. The silane-hydrogen-terminated silane-arylene resin prepared by this invention exhibits excellent heat resistance, possessing a very high thermal decomposition temperature of 5% weight loss in both nitrogen and air, and demonstrates superior processing performance with an extremely wide processing temperature window.

[0006] The objective of this invention can be achieved through the following technical solutions: The first aspect of the present invention provides a silane-containing aromatic resin with a silane-terminated hydrosilane, the structural formula of which is as follows: In the formula, R1 and R2 are independently CH3, CH2=CH, H or phenyl, respectively; n = 1~9.

[0007] In some specific embodiments, R1 and R2 are preferably CH3, CH2=CH, or H, and R1 and R2 are more preferably CH3 or H.

[0008] In some specific embodiments, the average degree of polymerization of the silane-terminated silane-acetylenic resin is 1 to 6, more preferably 3.432.

[0009] In some specific embodiments, the silane-terminated silane-aryl resin has at least one of the following structural formulas: , , , , , , , , , .

[0010] A second aspect of the present invention provides a method for preparing a silane-containing aromatic resin with silane end-capped silicon, comprising the following steps: S1: 1,3-Diethynylbenzene was reacted with Grignard reagent to give compound 1 as shown in Formula I; S2: Compound 1 is polymerized with compound 2 as shown in Formula II to obtain compound 3 as shown in Formula III; S3: Compound 3 is reduced with lithium aluminum hydride to obtain the silane-containing aromatic resin with silane-hydrogen end capping.

[0011] In some specific embodiments, in step S1, the Grignard reagent is selected from at least one of ethyl magnesium bromide, methyl magnesium bromide, ethyl magnesium chloride, or methyl magnesium chloride; the molar ratio of the Grignard reagent to 1,3-diethynylbenzene is 1:0.5.

[0012] In some specific embodiments, the 1,3-diethynylbenzene is added to the reaction system by dropwise addition.

[0013] In some specific embodiments, in step S1, the reaction temperature is 67~69 ℃, the reaction time is 1~3 h, and the reaction atmosphere is nitrogen or an inert gas.

[0014] In some specific embodiments, in step S2, the molar ratio of 1,3-diethynylbenzene to compound 2 is 1:(1~2), preferably 1:(1.1~2), more preferably 2:3~6:7, and even more preferably 1:1.1, 1:1.2, 1:1.25, 1:1.33, 1:1.5 or 1:2; compound 2 is selected from at least one of dimethyldichlorosilane, methylvinyldichlorosilane, methyldichlorosilane or methylphenyldichlorosilane; preferably, compound 2 is a mixture of methylvinyldichlorosilane and methyldichlorosilane in a molar ratio of 1:2~2:1, preferably 1:1, 1:2 or 2:1.

[0015] In some specific embodiments, compound 2 is added to the reaction system by dropwise addition.

[0016] In some specific embodiments, in step S2, the polymerization reaction is carried out at a temperature of 69-71°C for 1-3 hours, and the reaction atmosphere is nitrogen or an inert gas.

[0017] In some specific embodiments, the polymerization reaction time can be monitored for completion using conventional methods in the art, such as by judging the reaction completion by the change of reactants from precipitate to orange solution, or by monitoring with gas chromatography.

[0018] In some specific embodiments, in step S3, the molar ratio of 1,3-diethynylbenzene to lithium aluminum hydride is 2:1.

[0019] In some specific embodiments, the lithium aluminum hydride is added dropwise to the reaction system in the form of a solution, and the concentration of the dropwise solution containing the lithium aluminum hydride is 20~100 g / L, preferably 38~95 g / L; the dropwise addition time is 2~40 min; during the dropwise addition, the temperature of the reaction system is controlled at -20~20℃, preferably -10~10℃, and more preferably 0℃.

[0020] In some specific embodiments, in step S3, the reduction reaction is carried out at a temperature of -20 to 60 °C, preferably -20 to 20 °C, and more preferably 10 °C; the reaction time can be monitored by gas chromatography, specifically 6 to 24 h, preferably 6 to 12 h, and the reaction atmosphere is nitrogen or an inert gas.

[0021] In some specific embodiments, the reduction reaction is terminated by a terminator, which is water or an acid solution. The terminator is added at a temperature of -20 to 20°C, and the mixing time is 0.5 to 2 hours. The acid is selected from hydrochloric acid or acetic acid, with a concentration of 2 to 20 wt%, preferably 5 to 10 wt%.

[0022] In some specific embodiments, after the reaction is terminated, post-processing is performed, which specifically includes: extraction, washing, solvent removal and drying in sequence.

[0023] In some specific embodiments, the extractant used in the extraction is a halohydrocarbon or aromatic hydrocarbon, preferably dichloromethane or toluene; The washing includes rinsing with water until neutral; Before removing the solvent, water is first removed, and the dehydrating agent used is anhydrous sodium sulfate; The solvent removal includes vacuum distillation; The drying process is vacuum drying, with a drying temperature of 40~80℃, preferably 60℃, and a drying time of 2~12 h, preferably 6 h.

[0024] In some specific embodiments, in the Grignard reaction, polymerization reaction, and reduction reaction, the reaction solvent is preferably selected from one of ether solvents, haloalkanes solvents, or aromatic solvents; the mass-to-volume ratio of compound 2 to the reaction solvent is preferably 50-200 g / L, more preferably 60-100 g / L, and even more preferably 66 g / L, 72 g / L, or 78 g / L.

[0025] Preferably, the ether solvent is selected from one or a combination of two of tetrahydrofuran or methyltetrahydrofuran, preferably methyltetrahydrofuran; the halohydrocarbon solvent is dichloromethane; and the aromatic hydrocarbon solvent is toluene.

[0026] A third aspect of the present invention provides an application of a silane-containing aromatic resin with silane end-capped by silane, comprising using the silane-containing aromatic resin with silane end-capped by silane to prepare a heat-resistant structure.

[0027] Compared with the prior art, the present invention has the following beneficial effects: Excellent heat resistance, maintaining superior mechanical properties even at high temperatures: ① Extremely high glass transition temperature, exceeding 800 ℃; ② High weight loss temperature and high high-temperature residue rate in nitrogen and air. The resin cured product exhibits a 5% weight loss temperature of up to 690 ℃ in nitrogen, and a residue rate of up to 91% at 1000 ℃. The resin cured product exhibits a 5% weight loss temperature of up to 591 ℃ in air, and a residue rate of up to 53% at 800 ℃.

[0028] Excellent processing performance: The silicone-containing aromatic resin prepared by this invention has adjustable viscosity, with a viscosity of less than 0.3 Pa·s in the range of 40-120 ℃, which is used for resin transfer molding process, and a viscosity of more than 100 Pa·s in the range of 30 ℃, which is used for prepreg molding process. Therefore, the silane-containing aromatic resin of the present invention can be used as a high-temperature resistant resin matrix and has broad application prospects in high-tech fields such as aviation and aerospace. Attached Figure Description

[0029] Figure 1 It is a silane-terminated silane-side group-containing silane-arytyn resin (PSA-HH). 1 H-NMR MRI; Figure 2 It is a silane-terminated silane-side group-containing silane-arytyn resin (PSA-HH). 29 Si-NMR nuclear magnetic resonance image; Figure 3 This is the Fourier Transform Infrared (FT-IR) spectrum of a silane-containing arylene resin (PSA-HH) with silane-terminated silane-side groups. Figure 4 This is a differential scanning calorimetry (DSC) curve of a silane-containing arylene resin (PSA-HH) with silane-terminated silane-side groups. Figure 5 It is a silane-terminated vinyl-side group silane-containing resin (PSA-VH). 1 H-NMR MRI; Figure 6 It is a silane-terminated vinyl-side group silane-containing resin (PSA-VH). 29 Si-NMR nuclear magnetic resonance image; Figure 7 This is the Fourier Transform Infrared (FT-IR) spectrum of a silane-containing resin (PSA-VH) with silane-terminated vinyl side groups; Figure 8 This is a differential scanning calorimetry (DSC) chromatogram of a silane-containing resin (PSA-VH) with silane-terminated vinyl side groups; Figure 9 These are the viscosities at different temperatures of silane-terminated silane-terminated resin (PSA-HH-2) and silane-terminated vinyl-terminated resin (PSA-VH-2).

[0030] Figure 10 Viscosity of silane-terminated vinyl-side group resin (PSA-VH-5) at different temperatures.

[0031] Figure 11 These are TGA images of the thermosetting products of hydrogen silane-terminated silane-terminated resin (PSA-HH-2) and hydrogen silane-terminated vinyl-terminated silane-terminated resin (PSA-VH-2) under a nitrogen atmosphere.

[0032] Figure 12 These are TGA images of the thermosetting products of hydrogen silane-terminated silane-terminated resin (PSA-HH-2) and hydrogen silane-terminated vinyl-terminated silane-terminated resin (PSA-VH-2) in air atmosphere. Detailed Implementation

[0033] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0034] The following are more detailed implementation examples, which further illustrate the technical solution of the present invention and the technical effects that can be obtained.

[0035] In the following embodiments, unless otherwise specified, the raw materials, reagents or processing techniques are all conventional commercial products or conventional processing techniques in the art.

[0036] Example 1: PSA-HH-2, a silane-containing aromatic yne resin with silane-terminated silane-side groups, and its preparation method The specific implementation method includes the following steps: (1) Grignard reaction: First, under a nitrogen atmosphere, add 500 mL of 2 mol / L tetrahydrofuran solution of magnesium ethyl bromide to a 1L reactor equipped with a stirrer, thermometer, constant pressure funnel and condenser; then, slowly add 63.1 g of 1,3-diethynylbenzene (0.5 mol) dropwise through the feed port via a separatory funnel. After the addition is completed within 20-30 min, heat the mixture at 67-69 °C and reflux for about 2 h.

[0037] (2) Polymerization reaction: The reaction solution was cooled to below room temperature using an ice-water bath. 86.3 g of methyldichlorosilane (0.75 mol) was added through a separatory funnel. After the addition was completed in 5-10 min, the mixture was heated to reflux at 69-71 °C for about 2 h. The molar ratio of 1,3-diethynylbenzene to methyldichlorosilane was 2:3. (3) Reduction reaction: The reaction solution was cooled to below 10 °C using an ice-water bath, and 100 mL of 2.5 mol / L lithium aluminum hydride solution was added through a separatory funnel. After the addition was completed within 20-30 min, the reaction was carried out at 60 °C for about 24 h.

[0038] The specific reaction route is as follows: (4) Post-treatment: After the reaction is complete, the reaction solution is cooled to below room temperature using an ice-water bath, and then the reaction solution is poured into 1.5 L of 5 wt% hydrochloric acid solution and stirred for 1 h.

[0039] Then, 500 mL of dichloromethane was added for extraction. After standing, the mixture was washed with deionized water until nearly neutral, and the lower organic phase was separated. The mixture was dried with anhydrous Na₂SO₄, filtered, and the solvent was removed by vacuum distillation to obtain the final product. The yield was 79.1%, and the resin was an orange-yellow liquid. It is soluble in solvents such as tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, toluene, dioxane, and dichloromethane.

[0040] like Figure 1 As shown, PSA-HH-2 1 H-NMR (CDCl3): 4.14 ppm is the chemical shift value of terminal Si-H, 4.60 ppm is the chemical shift value of Si-H inside the molecular chain, and 7.22-7.71 ppm is the chemical shift value of hydrogen in the benzene ring.

[0041] like Figure 2 As shown, PSA-HH-2 29 Si-NMR (CDCl3): -60.09 ppm is the chemical shift value of terminal Si, and -60.04 ppm is the chemical shift value of Si inside the molecular chain.

[0042] like Figure 3 As shown, the FT-IR of PSA-HH-2 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 890 cm⁻¹ -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0043] like Figure 4 As shown, the initial curing temperature of PSA-HH-2 is 210℃, the peak temperature is 251℃, and the final curing temperature is 275℃. After PSA-HH-2 is cured sequentially at 170℃ / 2h-210℃ / 2h-250℃ / 4h, a dense and glossy black solid is obtained.

[0044] like Figure 9 As shown, PSA-HH-2 has a viscosity of less than 0.3 Pa·s at 40-120℃, making it suitable for RTM molding processes.

[0045] like Figure 11 As shown, the thermal decomposition temperature (5% thermal weight loss) of the PSA-HH-2 thermosetting product in a nitrogen atmosphere is 684°C, and the pyrolysis residue rate at 1000°C is 91.3%.

[0046] like Figure 12 As shown, the PSA-HH-2 thermosetting product has a thermal decomposition temperature (5% weight loss) of 591°C in air atmosphere and a pyrolysis residue rate of 53.6% at 800°C, exhibiting excellent high-temperature oxidation resistance.

[0047] Example 2: The following formula describes the silane-hydrogen-terminated vinyl-side group silane-arylene resin PSA-HH-3 The synthesis method differs from Example 1 only in that the molar ratio of 1,3-diethynylbenzene to methyldichlorosilane is 3:4. All other steps are the same as in Example 1. The yield of the final product was 79.8%.

[0048] like Figure 1 As shown, PSA-HH-3 1 ¹H-NMR (CDCl₃): 4.14 ppm is the chemical shift value of terminal Si-H, 4.60 ppm is the chemical shift value of Si-H within the molecular chain, and 7.22-7.71 ppm is the chemical shift value of hydrogen atoms in the benzene ring. The peak area ratio of the three is 2.07:1.00:6.20, which is close to the theoretical ratio of 2:1:6.

[0049] like Figure 2 As shown, PSA-HH-3's 29 Si-NMR (CDCl3): -60.09 ppm is the chemical shift value of terminal Si, and -60.04 ppm is the chemical shift value of Si within the molecular chain. The peak area ratio of the two is 1.00:1.14, which is close to the theoretical ratio of 1:1.

[0050] like Figure 3 As shown, the FT-IR of PSA-HH-3 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 890 cm⁻¹ -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0051] like Figure 4 As shown, the initial curing temperature of PSA-HH-3 is 210℃, the peak temperature is 251℃, and the final curing temperature is 275℃. After PSA-HH-3 is cured sequentially at 170℃ / 2h-210℃ / 2h-250℃ / 4h, a dense and glossy black solid is obtained.

[0052] Example 3: The following formula describes the silane-hydrogen-terminated vinyl-side group-containing silane-arytyn resin PSA-HH-4 The synthesis method differs from Example 1 only in that the molar ratio of 1,3-diethynylbenzene to methyldichlorosilane is 4:5. All other steps are the same as in Example 1. The yield of the final product was 80.8%.

[0053] like Figure 1 As shown, PSA-HH-4's 1 ¹H-NMR (CDCl₃): 4.14 ppm is the chemical shift value of terminal Si-H, 4.60 ppm is the chemical shift value of Si-H within the molecular chain, and 7.22-7.71 ppm is the chemical shift value of hydrogen atoms in the benzene ring. The peak area ratio of the three is 1.22:1.00:6.04, which is close to the theoretical ratio of 4:3:16.

[0054] like Figure 2 As shown, PSA-HH-4's 29 Si-NMR (CDCl3): -60.09 ppm is the chemical shift value of terminal Si, and -60.04 ppm is the chemical shift value of Si within the molecular chain. The peak area ratio of the two is 1.00:1.62, which is close to the theoretical ratio of 1:1.5.

[0055] like Figure 3 As shown, the FT-IR of PSA-HH-4 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 890 cm⁻¹ -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0056] like Figure 4 As shown, the initial curing temperature of PSA-HH-4 is 210℃, the peak temperature is 251℃, and the final curing temperature is 275℃. After PSA-HH-4 is cured sequentially at 170℃ / 2h-210℃ / 2h-250℃ / 4h, a dense and glossy black solid is obtained.

[0057] Example 4: The following formula describes the silane-hydrogen-terminated vinyl-side group-containing silane-arytyn resin PSA-HH-5 The synthesis method differs from Example 1 only in that the molar ratio of 1,3-diethynylbenzene to methyldichlorosilane is 5:6. All other steps are the same as in Example 1. The yield of the final product was 82.5%.

[0058] like Figure 1 As shown, PSA-HH-5 1 H-NMR (CDCl3): 4.14 ppm is the chemical shift value of terminal Si-H, 4.60 ppm is the chemical shift value of Si-H inside the molecular chain, and 7.22-7.71 ppm is the chemical shift value of hydrogen in the benzene ring.

[0059] like Figure 2 As shown, PSA-HH-5 29 Si-NMR (CDCl3): -60.09 ppm is the chemical shift value of terminal Si, and -60.04 ppm is the chemical shift value of Si within the molecular chain. The peak area ratio of the two is 1.00:2.14, which is close to the theoretical ratio of 1:2.

[0060] like Figure 3 As shown, the FT-IR of PSA-HH-5 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 890 cm⁻¹ -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0061] like Figure 4 As shown, the initial curing temperature of PSA-HH-5 is 210℃, the peak temperature is 251℃, and the final curing temperature is 275℃. After PSA-HH-5 is cured sequentially at 170℃ / 2h-210℃ / 2h-250℃ / 4h, a dense and glossy black solid is obtained.

[0062] Example 5: The following formula describes the silane-terminated vinyl-side group-containing silane-acetylenic resin PSA-HH-6 The synthesis method differs from Example 1 only in that the molar ratio of 1,3-diethynylbenzene to methyldichlorosilane is 6:7. All other steps are the same as in Example 1. The yield of the final product was 81.7%.

[0063] like Figure 1 As shown, PSA-HH-6 1 H-NMR (CDCl3): 4.14 ppm is the chemical shift value of terminal Si-H, 4.60 ppm is the chemical shift value of Si-H inside the molecular chain, and 7.22-7.71 ppm is the chemical shift value of hydrogen in the benzene ring.

[0064] like Figure 2 As shown, PSA-HH-6 29Si-NMR (CDCl3): -60.09 ppm is the chemical shift value of terminal Si, and -60.04 ppm is the chemical shift value of Si inside the molecular chain.

[0065] like Figure 3 As shown, the FT-IR of PSA-HH-6 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 890 cm⁻¹ -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0066] like Figure 4 As shown, the initial curing temperature of PSA-HH-6 is 210℃, the peak temperature is 251℃, and the final curing temperature is 275℃. After PSA-HH-6 is cured sequentially at 170℃ / 2h-210℃ / 2h-250℃ / 4h, a dense and glossy black solid is obtained.

[0067] Example 6: PSA-VH-2, a silane-containing aromatic yne resin with silane-terminated vinyl side groups and its preparation method The specific implementation method includes the following steps: (1) Grignard reaction: First, under a nitrogen atmosphere, add 500 mL of 2 mol / L tetrahydrofuran solution of magnesium ethyl bromide to a 1L reactor equipped with a stirrer, thermometer, constant pressure funnel and condenser; then, slowly add 63.1 g of 1,3-diethynylbenzene (0.5 mol) dropwise through the feed port via a separatory funnel. After the addition is completed within 20-30 min, heat the mixture at 67-69 °C and reflux for about 2 h.

[0068] (2) Polymerization reaction: The reaction solution was cooled to below room temperature using an ice-water bath. 105.8 g of methylvinyl dichlorosilane (0.75 mol) was added through a separatory funnel. After the addition was completed in 5-10 min, the mixture was heated to reflux at 69-71 °C for about 2 h. The molar ratio of 1,3-diethynylbenzene to methyl dichlorosilane was 2:3. (3) Reduction reaction: The reaction solution was cooled to below 10°C using an ice-water bath, and 100 mL of 2.5 mol / L lithium aluminum hydride solution was added through a separatory funnel. After the addition was completed within 20-30 min, the reaction was carried out at 60°C for about 24 h.

[0069] The specific reaction route is as follows: (4) Post-treatment: After the reaction is complete, the reaction solution is cooled to below room temperature using an ice-water bath, and then the reaction solution is poured into 1.5 L of 5wt% hydrochloric acid solution and stirred for 1 h.

[0070] Then, 500 mL of dichloromethane was added for extraction. After standing, the mixture was washed with deionized water until nearly neutral, and the lower organic phase was separated. Anhydrous Na₂SO₄ was added for drying, followed by filtration and vacuum distillation to remove the solvent, yielding the final product. The yield was 81.2%, and the resin was an orange-yellow liquid. It is soluble in solvents such as tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, toluene, dioxane, and dichloromethane.

[0071] like Figure 5 As shown, PSA-VH-2 1 H-NMR (CDCl3): 4.42 ppm is the chemical shift value of the terminal Si-H, 5.90-6.30 ppm is the chemical shift value of the hydrogen on the vinyl group, and 7.16-7.73 ppm is the chemical shift value of the hydrogen on the benzene ring.

[0072] like Figure 6 As shown, PSA-VH-2 29 Si-NMR (CDCl3): -42.07 ppm is the chemical shift value of terminal Si, and -46.06 ppm is the chemical shift value of Si inside the molecular chain.

[0073] like Figure 7 As shown, the FT-IR of PSA-VH-2 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 947 cm⁻¹ -1 The absorption peak at 890 cm⁻¹ corresponds to the out-of-plane oscillation vibration of the =CH₂ group. -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0074] like Figure 8 As shown, the initial curing temperature of PSA-VH-2 is 210℃, the peak temperature is 280℃, and the final curing temperature is 312℃. After PSA-VH-2 is cured sequentially at 180℃ / 2h-210℃ / 2h-240℃ / 2h-270℃ / 4h, a dense and glossy black solid is obtained.

[0075] like Figure 9 As shown, the viscosity of PSA-VH-2 is less than 1.8 Pa·s at 30-120℃.

[0076] like Figure 11As shown, the thermal decomposition temperature (5% thermal weight loss) of the PSA-VH-2 thermosetting product in a nitrogen atmosphere is 622°C, and the pyrolysis residue rate at 1000°C is 89%.

[0077] like Figure 12 As shown, the PSA-VH-2 thermosetting product has a thermal decomposition temperature (5% thermal weight loss) of 564°C in air atmosphere and a pyrolysis residue rate of 39.7% at 800°C.

[0078] Example 7 The following formula describes the silane-terminated vinyl-side group silane-containing arylene resin PSA-VH-3 The synthesis method differs from Example 1 only in that the molar ratio of 1,3-diethynylbenzene to methylvinyldichlorosilane is 3:4. All other steps are the same as in Example 1. The yield of the final product was 82.1%.

[0079] like Figure 5 As shown, PSA-VH-3 1 H-NMR (CDCl3): 4.42 ppm is the chemical shift value of the terminal Si-H, 5.90-6.30 ppm is the chemical shift value of the hydrogen on the vinyl group, and 7.16-7.73 ppm is the chemical shift value of the hydrogen on the benzene ring.

[0080] like Figure 6 As shown, PSA-VH-3 29 Si-NMR (CDCl3): -42.07 ppm is the chemical shift value of terminal Si, and -46.06 ppm is the chemical shift value of Si inside the molecular chain.

[0081] like Figure 7 As shown, the FT-IR of PSA-VH-3 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 947 cm⁻¹ -1 The absorption peak at 890 cm⁻¹ corresponds to the out-of-plane oscillation vibration of the =CH₂ group. -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0082] like Figure 8 As shown, the initial curing temperature of PSA-VH-3 is 210℃, the peak temperature is 280℃, and the final curing temperature is 312℃. After PSA-VH-3 is cured sequentially at 180℃ / 2h-210℃ / 2h-240℃ / 2h-270℃ / 4h, a dense and glossy black solid is obtained.

[0083] Example 8 The following formula describes the silane-terminated vinyl-side group silane-containing aromatic resin PSA-VH-4 The synthesis method differs from Example 1 only in that the molar ratio of 1,3-diethynylbenzene and methylvinyldichlorosilane is 4:5. All other steps are the same as in Example 1. The yield of the final product was 80.4%.

[0084] like Figure 5 As shown, PSA-VH-4 1 H-NMR (CDCl3): 4.42 ppm is the chemical shift value of the terminal Si-H, 5.90-6.30 ppm is the chemical shift value of the hydrogen on the vinyl group, and 7.16-7.73 ppm is the chemical shift value of the hydrogen on the benzene ring.

[0085] like Figure 6 As shown, PSA-VH-4 29 Si-NMR (CDCl3): -42.07 ppm is the chemical shift value of terminal Si, and -46.06 ppm is the chemical shift value of Si inside the molecular chain.

[0086] like Figure 7 As shown, the FT-IR of PSA-VH-4 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 947 cm⁻¹ -1 The absorption peak at 890 cm⁻¹ corresponds to the out-of-plane oscillation vibration of the =CH₂ group. -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0087] like Figure 8 As shown, the initial curing temperature of PSA-VH-4 is 210℃, the peak temperature is 280℃, and the final curing temperature is 312℃. After PSA-VH-4 is cured sequentially at 180℃ / 2h-210℃ / 2h-240℃ / 2h-270℃ / 4h, a dense and glossy black solid is obtained.

[0088] Example 9 The following formula describes the silane-terminated vinyl-side group-containing silane-acetylenic resin PSA-VH-5 The synthesis method differs from Example 1 only in that the molar ratio of 1,3-diethynylbenzene and methylvinyldichlorosilane is 5:6. All other steps are the same as in Example 1. The yield of the final product was 81.6%.

[0089] like Figure 5 As shown, PSA-VH-5 1 ¹H-NMR (CDCl₃): 4.42 ppm is the chemical shift value of the terminal Si-H group, 5.90-6.30 ppm is the chemical shift value of the hydrogen on the vinyl group, and 7.16-7.73 ppm is the chemical shift value of the hydrogen on the benzene ring. The peak area ratio of the three groups is 1.00:8.92:10.11, which is close to the theoretical ratio of 1:9:10.

[0090] like Figure 6 As shown, PSA-VH-5 29 Si-NMR (CDCl3): -42.07 ppm is the chemical shift value of terminal Si, and -46.06 ppm is the chemical shift value of Si within the molecular chain. The peak area ratio of the two is 1.00:2.07, which is close to the theoretical ratio of 1:2.

[0091] like Figure 7 As shown, the FT-IR of PSA-VH-5 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 947 cm⁻¹ -1 The absorption peak at 890 cm⁻¹ corresponds to the out-of-plane oscillation vibration of the =CH₂ group. -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0092] like Figure 8 As shown, the initial curing temperature of PSA-VH-5 is 210℃, the peak temperature is 280℃, and the final curing temperature is 312℃. After PSA-VH-5 is cured sequentially at 180℃ / 2h-210℃ / 2h-240℃ / 2h-270℃ / 4h, a dense and glossy black solid is obtained.

[0093] like Figure 10 As shown, PSA-VH-5 has a viscosity exceeding 100 Pa·s at 30℃ and can be used with prepreg process.

[0094] Example 10 The following formula describes the silane-terminated vinyl-side group-containing silane-acetylenic resin PSA-VH-6 The synthesis method differs from Example 1 only in that the molar ratio of 1,3-diethynylbenzene to methylvinyldichlorosilane is 6:7. All other aspects are the same as in Example 1. The yield of the final product was 82.6%.

[0095] like Figure 5As shown, PSA-VH-5 1 H-NMR (CDCl3): 4.42 ppm is the chemical shift value of the terminal Si-H, 5.90-6.30 ppm is the chemical shift value of the hydrogen on the vinyl group, and 7.16-7.73 ppm is the chemical shift value of the hydrogen on the benzene ring.

[0096] like Figure 6 As shown, PSA-VH-5 29 Si-NMR (CDCl3): -42.07 ppm is the chemical shift value of terminal Si, and -46.06 ppm is the chemical shift value of Si inside the molecular chain.

[0097] like Figure 7 As shown, the FT-IR of PSA-VH-5 is 2155 cm⁻¹. -1 The stretching vibration is of the form -C≡C-, 1255cm. -1 This is a stretching vibration of Si-CH3, 947 cm⁻¹ -1 The absorption peak at 890 cm⁻¹ corresponds to the out-of-plane oscillation vibration of the =CH₂ group. -1 The absorption peak at 1592 cm⁻¹ corresponds to the bending vibration of the Si-H bond. -1 The absorption peak at that point corresponds to the vibration of the benzene ring skeleton.

[0098] like Figure 8 As shown, the initial curing temperature of PSA-VH-6 is 210℃, the peak temperature is 280℃, and the final curing temperature is 312℃. After PSA-VH-6 is cured sequentially at 180℃ / 2h-210℃ / 2h-240℃ / 2h-270℃ / 4h, a dense and glossy black solid is obtained.

[0099] Comparative Example 1: PSA-H silane-containing resin The preparation method includes the following steps: (1) Grignard reaction: First, under a nitrogen atmosphere, add 500 mL of 2 mol / L tetrahydrofuran solution of magnesium ethyl bromide to a 1L reactor equipped with a stirrer, thermometer, constant pressure funnel and condenser; then, slowly add 63.1 g of 1,3-diethynylbenzene (0.5 mol) dropwise through the feed port via a separatory funnel. After the addition is completed within 20-30 min, heat the mixture at 67-69 °C and reflux for about 2 h.

[0100] (2) Polymerization reaction: The reaction solution was cooled to below room temperature using an ice-water bath. 38.3 g of methylvinyl dichlorosilane (0.33 mol) was added through a separatory funnel. After the addition was completed in 5-10 min, the mixture was heated to reflux at 69-71 °C for about 2 h. The molar ratio of 1,3-diethynylbenzene to methyl dichlorosilane was 3:2. The specific reaction route is as follows: (3) Post-treatment: After the reaction is complete, the reaction solution is cooled to below room temperature using an ice-water bath, and 100 mL of acetic acid is added to the reaction solution and stirred for 1 hour.

[0101] Then, 400 mL of dichloromethane was added for extraction. After standing, the mixture was washed with deionized water until nearly neutral, and the lower organic phase was separated. The mixture was dried over anhydrous Na₂SO₄, filtered, and the solvent was removed by vacuum distillation to obtain the final product. The yield was 79.1%, and the resin was an orange-yellow liquid. It is soluble in solvents such as tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, toluene, dioxane, and dichloromethane.

[0102] Its 5% decomposition temperature in air is 527℃.

[0103] Comparative Example 2: PSA-V Resin Containing Silaneyne The preparation method includes the following steps: (1) Grignard reaction: First, under a nitrogen atmosphere, add 500 mL of 2 mol / L tetrahydrofuran solution of magnesium ethyl bromide to a 1L reactor equipped with a stirrer, thermometer, constant pressure funnel and condenser; then, slowly add 63.1 g of 1,3-diethynylbenzene (0.5 mol) dropwise through the feed port via a separatory funnel. After the addition is completed within 20-30 min, heat the mixture at 67-69 °C and reflux for about 2 h.

[0104] (2) Polymerization reaction: The reaction solution was cooled to below room temperature using an ice-water bath. 105.8 g of methyl vinyl dichlorosilane (0.75 mol) was added through a separatory funnel. After the addition was completed in 5-10 min, the mixture was heated to reflux at 69-71 °C for about 2 h. The feed ratio of 1,3-diethynylbenzene to methyl vinyl dichlorosilane was 3:2. The specific reaction route is as follows: (3) Post-treatment: After the reaction is complete, the reaction solution is cooled to below room temperature using an ice-water bath, and 100 mL of acetic acid is added to the reaction solution and stirred for 1 hour.

[0105] Then, 400 mL of dichloromethane was added for extraction. After standing, the mixture was washed with deionized water until nearly neutral, and the lower organic phase was separated. The mixture was dried over anhydrous Na₂SO₄, filtered, and the solvent was removed by vacuum distillation to obtain the final product. The yield was 78.2%, and the resin was an orange-yellow liquid. It is soluble in solvents such as tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, toluene, dioxane, and dichloromethane.

[0106] Its 5% decomposition temperature in air is 513℃.

[0107] The silane-containing aromatic yne resin prepared by this invention exhibits superior high-temperature oxidation resistance compared to traditional silane-containing aromatic yne resins with acetylation hydrogen-terminated resins. For example, it possesses an extremely high thermal decomposition temperature (591°C) and mass retention rate (53.6%) at 800°C in air, representing a 60°C increase in thermal decomposition temperature and a 26.9% increase in mass retention rate compared to traditional dimethyl silane-containing aromatic yne resins with a 5% weight loss. Furthermore, it exhibits excellent processing performance; by adjusting its structure and molecular weight, it can be adapted to various molding processes. It can serve as a high-temperature resistant composite resin matrix and has broad application prospects in high-tech fields such as aerospace and aviation.

[0108] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A silane-terminated hydroxyl-capped resin containing silane, characterized in that, The structural formula is as follows: In the formula, R1 and R2 are independently CH3, CH2=CH, H or phenyl, respectively; n = 1~9.

2. The silane-terminated silane-containing aromatic resin according to claim 1, characterized in that, It has at least one of the following structural formulas: 、 、 、 、 、 、 、 、 、 。 3. A method for preparing a silane-containing aromatic resin with silane hydrothionization as described in claim 1 or 2, characterized in that, Includes the following steps: S1: 1,3-Diethynylbenzene was reacted with Grignard reagent to give compound 1 as shown in Formula I; S2: Compound 1 is polymerized with compound 2 as shown in Formula II to obtain compound 3 as shown in Formula III; S3: Compound 3 is reduced with lithium aluminum hydride to obtain the silane-containing aromatic resin with silane-hydrogen end capping.

4. The method for preparing the silane-containing aromatic resin with silane end-capped by claim 3, characterized in that, In step S1, the Grignard reagent is selected from at least one of ethyl magnesium bromide, methyl magnesium bromide, ethyl magnesium chloride, or methyl magnesium chloride; the molar ratio of the Grignard reagent to 1,3-diethynylbenzene is 1:0.

5.

5. The method for preparing the silane-containing aromatic acetylenite resin with silane hydrothionization according to claim 3, characterized in that, In step S1, the reaction temperature is 67~69 ℃, the reaction time is 1~3 h, and the reaction atmosphere is nitrogen or an inert gas.

6. The method for preparing the silane-containing aromatic acetylenite resin with silane hydrothionization according to claim 3, characterized in that, In step S2, the molar ratio of 1,3-diethynylbenzene to compound 2 is 1:(1~2), preferably 2:3~6:7; compound 2 is selected from at least one of dimethyldichlorosilane, methylvinyldichlorosilane, methyldichlorosilane or methylphenyldichlorosilane.

7. The method for preparing the silane-containing aromatic resin with silane end-capped by claim 3, characterized in that, In step S2, the polymerization reaction is carried out at a temperature of 69-71 °C for 1-3 h, and the reaction atmosphere is nitrogen or an inert gas.

8. The method for preparing the silane-containing aromatic resin with silane end-capped by claim 3, characterized in that, In step S3, the molar ratio of 1,3-diethynylbenzene to lithium aluminum hydride is 2:

1.

9. The method for preparing the silane-containing aromatic acetylenite resin with silane hydrothionization according to claim 3, characterized in that, In step S3, the reduction reaction is carried out at a temperature of -20 to 60 °C for 6 to 24 h, and the reaction atmosphere is nitrogen or an inert gas.

10. An application of the silane-containing aromatic resin with silane end-capped as described in claim 9, characterized in that, The silane-terminated silane-containing arylene resin is used to prepare heat-resistant structures.

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