Silicon-containing aryl acetylene compound, preparation and curing method thereof, and silicon-containing aryl acetylene resin

Abstract

The present invention provides a silicon-containing aryl acetylene compound, a preparation and curing method thereof, and a silicon-containing aryl acetylene resin. The silicon-containing aryl acetylene compound has a structure as shown in Formula I, has a low curing temperature, and the cured product has high heat resistance.

Description

Technical Field

[0001] The invention relates to a silicon-containing aryl acetylene compound, a preparation and curing method thereof and a silicon-containing aryl acetylene resin. Background Art

[0002] Silicon-containing arylacetylene resin is a new type of organic-inorganic hybrid arylacetylene resin formed by introducing inorganic silicon elements into the main chain structure of organic arylacetylene polymers. This resin has excellent heat resistance and high-temperature ceramic properties, and is expected to be used as a high-temperature resistant polymer matrix in the aerospace field. At present, the main silicon-containing arylacetylene polymers are still mainly linear molecules, which form a cross-linked three-dimensional network structure after thermal curing. However, due to the presence of internal acetylene groups, silicon-containing arylacetylene polymers will inevitably require a higher curing temperature, with a peak curing temperature of about 210°C. And due to the influence of the linear structure, a large number of internal acetylene groups cannot be fully reacted, and the cross-linking density is low, resulting in its thermal properties cannot be fully exerted.

[0003] The branched molecular structure has a large number of functional groups at the end, and its polymer has lower viscosity and good solubility compared to linear structure molecules. The large number of functional groups at the end of the branched molecular structure can fully undergo a curing reaction and form a three-dimensional network structure with a high cross-linking density, which is beneficial to improve its heat resistance. Dai et al. described three new branched silicon-containing arylacetylene resins in "Star-shaped arylacetylene resins derived from silicon" Journal of Polymer Engineering, vol. 40, no. 8, 2020, pp. 676-684. The curing temperature range is between 140-274 ° C, Td 5％ The highest temperature can reach 697°C and it has a very low viscosity. Compared with linear silicon-containing aromatic acetylene resins, its heat resistance has been greatly improved.

[0004] Therefore, it is of great significance to study branched silicon-containing arylacene polymers. Summary of the invention

[0005] A first object of the present invention is to provide a compound having a low curing temperature and a cured product having high heat resistance.

[0006] The second object of the present invention is to provide a method for preparing the above compound.

[0007] The third object of the present invention is to provide a curing method for the above compound and a cured product, a silicon-containing arylacetylene resin.

[0008] In order to achieve the above object, the present invention adopts the following technical solution:

[0009] The present invention provides a silicon-containing aryl acetylene compound, the structure of which is shown in Formula I:

[0010]

[0011] Wherein, R is methyl, ethyl, vinyl or phenyl.

[0012] The present invention also provides a method for preparing the above silicon-containing aryl alkynyl compound, which comprises: subjecting the compound represented by formula II to a condensation reaction with the compound represented by formula III to obtain the above silicon-containing aryl alkynyl compound;

[0013]

[0014] Wherein, X is F, Cl, Br or I, and R is methyl, ethyl, vinyl or phenyl. Wherein, the compound represented by formula III is preferably trichlorosilane, such as methyltrichlorosilane, vinyltrichlorosilane or phenyltrichlorosilane.

[0015] The amount of the compound of formula II can be the conventional amount used in the condensation reaction in the art. For example, the molar ratio of the compound of formula II to the compound of formula III can be 3:0.99-1.

[0016] Wherein, the condensation reaction can be carried out in a solvent. The solvent can be an anhydrous solvent. The solvent can be at least one of an ether solvent (e.g., at least one of ether, tetrahydrofuran and methyltetrahydrofuran), an amide solvent (e.g., N,N-dimethylformamide, etc.), a ketone solvent (e.g., acetone, etc.), an aromatic hydrocarbon solvent (e.g., toluene, etc.) and a halogenated alkane solvent (e.g., dichloromethane, etc.), and the solvent does not react with the compound shown in Formula II.

[0017] Wherein, the reaction conditions of the condensation reaction may be conventional conditions of condensation reaction in the art. For example, the reaction temperature of the condensation reaction may be 60-70° C. For example, the reaction time of the condensation reaction may be 2-4 hours. For example, the reaction may be carried out under the protection of nitrogen or inert gas.

[0018] The specific steps of the preparation method of the silicon-containing aryl alkynyl compound may include: adding a solution of the compound of formula III to a solution of the compound of formula II at room temperature to carry out the condensation reaction. The room temperature is, for example, 10°C-15°C. The main purpose of setting the reaction temperature below room temperature is to prevent the compound of formula III from reacting directly and rapidly after being added, and lowering the temperature is to slow down the reaction rate during the dropwise addition process.

[0019] The method for preparing the silicon-containing aryl alkynyl compound further comprises post-treatment. The post-treatment may include: adding an acid to the reaction system to terminate the reaction, extracting (for example, using methyl tert-butyl ether or dichloromethane), separating the liquids, washing (for example, using deionized water) to neutrality, and removing the solvent (for example, by reduced pressure distillation) to obtain the silicon-containing aryl alkynyl compound.

[0020] In the present invention, the preparation method of the compound shown in formula II comprises: reacting alkyl magnesium bromide with triethynylbenzene to obtain the compound shown in formula II.

[0021] Wherein, the alkyl magnesium bromide can be ethyl magnesium bromide, etc. The reaction of ethyl magnesium bromide and triethynylbenzene is as follows:

[0022]

[0023] The amount of the alkylmagnesium bromide used may be a conventional amount used in this type of reaction in the art. For example, the molar ratio of the alkylmagnesium bromide to triethynylbenzene may be 1 to 1.01:1, for example 1:1.

[0024] Wherein, the reaction can be carried out in a solvent. The solvent can be an anhydrous solvent. The solvent can be at least one of an ether solvent (e.g., at least one of ether, tetrahydrofuran and methyltetrahydrofuran), an amide solvent (e.g., N,N-dimethylformamide, etc.), a ketone solvent (e.g., acetone, etc.), an aromatic hydrocarbon solvent (e.g., toluene, etc.) and a halogenated alkane solvent (e.g., dichloromethane, etc.), and the solvent does not react with the alkylmagnesium bromide and the compound shown in Formula II.

[0025] The reaction conditions of the reaction may be conventional conditions of this type of reaction in the art. For example, the reaction temperature of the reaction may be 60-70° C. For example, the reaction time of the reaction may be 2-4 hours. For example, the reaction may be carried out under the protection of nitrogen or inert gas.

[0026] The specific steps of the preparation method of the compound shown in Formula II may include: under the protection of nitrogen or inert gas, triethynylbenzene, alkylmagnesium bromide and solvent are mixed and reacted. The specific steps of mixing triethynylbenzene, alkylmagnesium bromide and solvent may include: adding alkylmagnesium bromide solution dropwise to the mixture of triethynylbenzene and solvent under ice water bath.

[0027] After the reaction, no post-treatment is required, and the obtained compound represented by formula II and the compound represented by formula III can be directly subjected to condensation reaction.

[0028] The specific steps of the preparation method of the silicon-containing aromatic alkynyl compound may include: mixing triethynylbenzene and anhydrous solvent and adding them to a reaction container protected by nitrogen or inert gas, dripping ethylmagnesium bromide solution into the reaction system under an ice-water bath, heating after the dripping is complete, and keeping the temperature at 60-70°C for reaction for 2-4 hours; cooling the reaction system to room temperature, dripping trichlorosilane into the system, heating to 60-70°C after the dripping is complete, and continuing the reaction for 2-4 hours, then adding acid to the system to terminate the reaction, stirring sufficiently, extracting with methyl tert-butyl ether or dichloromethane, separating the liquids, washing with deionized water until neutral, and removing the solvent by reduced pressure distillation to obtain the silicon-containing aromatic alkynyl compound.

[0029] The present invention also provides a method for curing the above silicon-containing aryl acetylene compound, which is characterized by comprising: curing the above silicon-containing aryl acetylene compound at a curing temperature of 130° C.-190° C. to obtain a silicon-containing aryl acetylene resin.

[0030] Wherein, the curing can be carried out in an air atmosphere.

[0031] Preferably, the curing temperature is 140°C-180°C. More preferably, the specific process of curing includes: keeping the above-mentioned silicon-containing aryl alkynyl compound at 135°C-145°C for 3-7 hours, keeping it at 145°C-155°C for 1-3 hours, and keeping it at 165°C-185°C for 2-6 hours. Further, the specific process of curing includes: keeping the above-mentioned silicon-containing aryl alkynyl compound at 135°C-145°C for 3-5 hours, keeping it at 145°C-155°C for 1-3 hours, keeping it at 165°C-175°C for 1-3 hours, and keeping it at 175°C-185°C for 2-4 hours; or, keeping the above-mentioned silicon-containing aryl alkynyl compound at 135°C-145°C for 5-7 hours, keeping it at 145°C-155°C for 1-3 hours, and keeping it at 175°C-185°C for 2-4 hours.

[0032] Wherein, the curing time can be 8-12 hours.

[0033] Wherein, during the curing process, the silicon-containing aryl acetylene compound is polymerized and cross-linked.

[0034] The present invention also provides a silicon-containing arylacetylene resin, which is prepared from the above-mentioned silicon-containing arylacetylene compound by the above-mentioned curing method.

[0035] The 5% thermal weight loss temperature of the silicon-containing aromatic acetylene resin in a nitrogen atmosphere can be 780° C.-849° C.

[0036] The present invention also provides a silicon-containing arylacetylene resin, which is obtained by polymerizing and cross-linking the above silicon-containing arylacetylene compound, wherein the 5% thermal weight loss temperature of the silicon-containing arylacetylene resin in a nitrogen atmosphere is 780°C-849°C.

[0037] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0038] The reagents and raw materials used in the present invention are commercially available.

[0039] The positive and progressive effects of the present invention are:

[0040] The silicon-containing aromatic acetylene compound of the present invention is soluble in many commonly used organic solvents, such as tetrahydrofuran, methyltetrahydrofuran, toluene, acetone, methyl tert-butyl ether, dichloromethane, N,N-dimethylformamide, etc., and has excellent process performance. It can form a dense solidified material by cross-linking and curing at a relatively low temperature, and no small molecules are released during curing. The solidified material has a highly cross-linked three-dimensional network structure and excellent thermal stability. It can be used to prepare high temperature resistant resins and advanced resin-based composite materials, and has great development prospects in the field of aerospace. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 It is the infrared spectra (FT-IR) of silicon-containing aryl acetylene compound (BSTEB) and comparative sample TEMPS;

[0042] Figure 2 The silicon-containing aryl acetylene compound (BSTEB) and the comparative sample TEMPS 1 H-NMR nuclear magnetic spectrum;

[0043] Figure 3 is the MALDI-TOF-MS mass spectra of the silicon-containing aryl acetylene compound (BSTEB) and the comparative sample TEMPS;

[0044] Figure 4 is the DSC graph of silicon-containing aryl acetylene compound (BSTEB) and comparative sample TEMPS;

[0045] Figure 5 It is the TGA graph of the thermally cured products of the silicon-containing aryl acetylene compound (BSTEB) and the comparative sample TEMPS under nitrogen atmosphere.

[0046] Figure 6 It is the infrared spectrum (FT-IR) of the silicon-containing aryl acetylene compound (BSTEB-H);

[0047] Figure 7 It is a silicon-containing aryl acetylene compound (BSTEB-H) 1 H-NMR nuclear magnetic spectrum;

[0048] Figure 8 is the MALDI-TOF-MS mass spectrum of the silicon-containing aryl acetylene compound (BSTEB-H);

[0049] Fig. 9 is the DSC graph of the silicon-containing aryl acetylene compound (BSTEB-H);

[0050] Fig.10 This is the TGA graph of the thermally cured product of the silicon-containing aryl acetylene compound (BSTEB-H) under nitrogen atmosphere. DETAILED DESCRIPTION

[0051] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0052] In the present invention, the structure of the silicon-containing aryl-alkynyl compound is characterized by infrared spectroscopy and nuclear magnetic resonance hydrogen spectrum (using deuterated DMSO as solvent), and the molecular weight is determined by time-of-flight mass spectrometry (MALDI-TOF-MS); the curing temperature range of the silicon-containing aryl-alkynyl compound is measured by differential scanning calorimetry (DSC), and the test is carried out in a N2 atmosphere at a heating rate of 5°C / min. The 5% thermal weight loss temperature (Td 5％ ) was tested by thermogravimetric analyzer in nitrogen atmosphere with a heating rate of 10°C / min.

[0053] Example 1

[0054] In a 500mL three-necked flask equipped with a nitrogen conduit, a dropper and a condenser, vacuum and nitrogen are replaced several times to dehumidify and deoxygenate. Under nitrogen protection, 4.505g (0.03mol) of 1,3,5-triethynylbenzene is dissolved in 50mL of anhydrous tetrahydrofuran and added to the three-necked flask, and 30.3mL of ethylmagnesium bromide / tetrahydrofuran solution (ethylmagnesium bromide is dissolved in anhydrous tetrahydrofuran, and the concentration of ethylmagnesium bromide is 1mol / L) is added dropwise in an ice-water bath environment, and the reaction is carried out at 68°C for 2 hours after the addition is complete. After the reaction is completed, the reaction system is cooled to below room temperature, and trichloromethylsilane / tetrahydrofuran solution (1.495g 0.01mol trichloromethylsilane is dissolved in 20mL of anhydrous tetrahydrofuran) is added thereto, and the condensation reaction is carried out at 68°C for 2 hours. The reaction was terminated with 50 mL of dilute hydrochloric acid (mass fraction 2%), a sufficient amount of methyl tert-butyl ether was added, and the organic phase was taken after washing with water until neutral. An excess of anhydrous sodium sulfate was added to the organic phase and allowed to stand for 12 hours. The precipitate was removed by filtration, and the filtrate was distilled off the solvent by a rotary evaporator to obtain a silicon-containing aromatic alkynyl compound (BSTEB-M) with a structure as shown in Formula I, wherein R is methyl, and the yield is 51.6%.

[0055] like Figure 1 As shown, FT-IR of BSTEB-M: 3382cm -1 The absorption peak of -C≡CH is 2166cm -1 A strong and sharp absorption peak of -C≡C- bond appears at 2965cm -1 is the stretching vibration absorption peak of CH in CH3, 1413 cm -1 and 1256cm -1 The symmetrical deformation vibration absorption peak of Si-CH3 is 3066cm- 1 The CH stretching vibration on the benzene ring is 1578 cm -1 It is the C=C stretching vibration of the benzene ring.

[0056] like Figure 2 As shown, BSTEB-M 1 H-NMR (C2D6SO): 4.38ppm is the chemical shift of terminal acetyl hydrogen, 7.59-7.82ppm is the chemical shift of benzene ring hydrogen, and 0.72ppm is the chemical shift of methyl hydrogen. The peak area ratio of the three is: A Si-CH3 :A -C≡CH :A -Ar-H =1:1.93:2.96, which is close to the theoretical ratio of 1:2:3.

[0057] BSTEB-M is a brown-yellow solid, soluble in tetrahydrofuran, methyltetrahydrofuran, toluene, acetone, N,N-dimethylformamide, dichloromethane and other solvents.

[0058] like Figure 3 As shown, the molecular weight was 490.1 as determined by time-of-flight mass spectrometry, indicating the presence of BSTEB-M in the product.

[0059] like Figure 4 As shown, in an air atmosphere, the above silicon-containing aryl acetylene compound was cured according to the following curing process: the initial curing temperature of BSTEB-M was 146.2°C, the peak value was 156.7°C, and the end temperature was 174.1°C. BSTEB-M was cured at 140°C / 4h→150°C / 2h→170°C / 2h→180°C / 3h in sequence to obtain a dense and shiny black solid.

[0060] like Figure 5 As shown, the thermal decomposition temperature (thermal weight loss 5%) of the BSTEB-M thermally cured product in a nitrogen atmosphere is 778°C, and the thermal decomposition residue rate at 800°C is 94.7%.

[0061] Example 2

[0062] In a 500mL three-necked flask equipped with a nitrogen conduit, a dropper and a condenser, vacuum and nitrogen are replaced several times to dehumidify and deoxygenate. Under nitrogen protection, 4.505g (0.03mol) of 1,3,5-triethynylbenzene is dissolved in 50mL of anhydrous tetrahydrofuran and added to the three-necked flask, and 30.3mL of ethylmagnesium bromide / tetrahydrofuran solution (ethylmagnesium bromide is dissolved in anhydrous tetrahydrofuran, and the concentration of ethylmagnesium bromide is 1mol / L) is added dropwise in an ice-water bath environment, and the reaction is carried out at 68°C for 2 hours after the addition is complete. After the reaction is completed, the reaction system is cooled to below room temperature, and trichlorophenylsilane / tetrahydrofuran solution (2.115g 0.01mol trichlorophenylsilane is dissolved in 20mL of anhydrous tetrahydrofuran) is added thereto, and the condensation reaction is carried out at 68°C for 2 hours. The reaction was terminated with 50 mL of dilute hydrochloric acid (mass fraction 2%), a sufficient amount of methyl tert-butyl ether was added, and the organic phase was taken after washing with water until neutral. An excess of anhydrous sodium sulfate was added to the organic phase and allowed to stand for 12 hours. The precipitate was removed by filtration, and the filtrate was distilled off the solvent by a rotary evaporator to obtain a silicon-containing aromatic alkynyl compound (BSTEB-B) with a structure as shown in Formula I, wherein R is phenyl, and the yield is 50.7%.

[0063] like Figure 1 As shown, FT-IR of BSTEB-B: 3290cm -1 The absorption peak of -C≡CH is 2165cm -1 A strong and sharp absorption peak of -C≡C- bond appears at 3069cm- 1 The CH stretching vibration on the benzene ring is 1578 cm -1 It is the C=C stretching vibration of the benzene ring.

[0064] like Figure 2 As shown, BSTEB-B 1 H-NMR (C2D6SO): 4.38ppm is the chemical shift of the terminal acetyl hydrogen, 7.59~7.82ppm is the chemical shift of the benzene ring hydrogen. The peak area ratio of the two is: -C≡CH :A -Ar-H =1:2.63, which is closer to the theoretical ratio of 1:2.33.

[0065] BSTEB-B is a brown-yellow solid, soluble in tetrahydrofuran, methyltetrahydrofuran, acetone, toluene, dimethylformamide, dichloromethane and other solvents.

[0066] like Figure 3 As shown, the molecular weight was 552.13 as determined by time-of-flight mass spectrometry, indicating the presence of BSTEB-B in the product.

[0067] like Figure 4As shown, in an air atmosphere, the above silicon-containing aryl acetylene compound was cured according to the following curing process: the starting curing temperature of BSTEB-B was 148.2°C, the peak value was 158.1°C, and the end temperature was 174.0°C. BSTEB-B was cured at 140°C / 4h→150°C / 2h→170°C / 2h→180°C / 3h in sequence to obtain a dense and shiny black solid.

[0068] like Figure 5 As shown, the thermal decomposition temperature (thermal weight loss 5%) of the BSTEB-B thermally cured product in a nitrogen atmosphere is 804°C, and the thermal decomposition residue rate at 800°C is 95.0%.

[0069] Example 3

[0070] In a 500mL three-necked flask equipped with a nitrogen conduit, a dropper and a condenser, the system was evacuated and replaced with nitrogen several times to remove moisture and oxygen. Under nitrogen protection, 4.505g (0.03mol) of 1,3,5-triethynylbenzene was dissolved in 50mL of anhydrous tetrahydrofuran and added to the three-necked flask. 30.3mL of ethylmagnesium bromide / tetrahydrofuran solution (ethylmagnesium bromide was dissolved in anhydrous tetrahydrofuran, and the concentration of ethylmagnesium bromide was 1mol / L) was added dropwise in an ice-water bath environment. After the addition, the system was kept warm at 68°C for 2 hours. After the reaction was completed, the reaction system was cooled to below room temperature, and trichlorovinylsilane / tetrahydrofuran solution (1.615g 0.01mol trichlorovinylsilane was dissolved in 20mL of anhydrous tetrahydrofuran) was added thereto, and the condensation reaction was carried out at 68°C for 2 hours. The reaction was terminated with 50 mL of dilute hydrochloric acid (mass fraction 2%), a sufficient amount of methyl tert-butyl ether was added, and the organic phase was taken after washing with water until neutral. An excess of anhydrous sodium sulfate was added to the organic phase and allowed to stand for 12 hours. The precipitate was removed by filtration, and the filtrate was distilled off the solvent by a rotary evaporator to obtain a silicon-containing aromatic alkynyl compound (BSTEB-V) as shown in Formula I, wherein R is vinyl, and the yield is 60%.

[0071] like Figure 1 As shown, FT-IR of BSTEB-V: 3290 cm -1 The absorption peak of -C≡CH is 2166cm -1 A strong and sharp absorption peak of -C≡C- bond appears at 3064cm- 1 is the CH stretching vibration on the benzene ring, 3015cm -1 It is the hydrogen vibration peak on -CH=CH2, 1579cm -1 It is the C=C stretching vibration peak of the benzene ring.

[0072] like Figure 2 As shown, BSTEB-V 1H-NMR (C2D6SO): 4.38ppm is the chemical shift value of the terminal acetylene hydrogen, 7.59-7.82ppm is the chemical shift value of the benzene ring hydrogen, and 6.1-6.4ppm is the chemical shift value of the vinyl group. The peak area ratio of the three is: -CH＝CH2 :A -C≡CH :A -Ar-H =1:1.95:3.01, which is close to the theoretical ratio of 1:2:3.

[0073] BSTEB-V is a brown-yellow solid, soluble in tetrahydrofuran, methyltetrahydrofuran, acetone, toluene, dimethylformamide, dichloromethane and other solvents.

[0074] like Figure 3 As shown, the molecular weight was 502.12 as determined by time-of-flight mass spectrometry, indicating the presence of BSTEB-V in the product.

[0075] like Figure 4 As shown, in an air atmosphere, the above silicon-containing aryl acetylene compound was cured according to the following curing process: the initial curing temperature of BSTEB-V was 143.7°C, the peak value was 154.4°C, and the end temperature was 170.2°C. BSTEB-V was cured at 140°C / 6h→150°C / 2h→→180°C / 3h to obtain a dense and bright black solid.

[0076] like Figure 5 As shown, the thermal decomposition temperature (thermal weight loss 5%) of the BSTEB-V thermally cured product in a nitrogen atmosphere is 849°C, and the thermal decomposition residue rate at 800°C is 96.2%.

[0077] Comparative Example 1

[0078] The silicon-containing aryl acetylene compound (BSTEB-H) described by the following formula:

[0079]

[0080] Its synthesis method is:

[0081] In a 500mL three-necked flask equipped with a nitrogen conduit, a dropper and a condenser, vacuum and nitrogen are replaced several times to dehumidify and deoxygenate. Under nitrogen protection, 4.505g (0.03mol) of 1,3,5-triethynylbenzene is dissolved in 50mL of anhydrous tetrahydrofuran and added to the three-necked flask, and 30.3mL of ethylmagnesium bromide / tetrahydrofuran solution (ethylmagnesium bromide is dissolved in anhydrous tetrahydrofuran, and the concentration of ethylmagnesium bromide is 1mol / L) is added dropwise in an ice-water bath environment. After the addition is completed, the reaction is kept at 68°C for 2 hours. After the reaction is completed, the reaction system is cooled to below room temperature, and trichlorosilane / tetrahydrofuran solution (1.354g 0.01mol trichlorosilane is dissolved in 20mL of anhydrous tetrahydrofuran) is added thereto, and the condensation reaction is kept at 68°C for 2 hours. The reaction was terminated with 50 mL of dilute hydrochloric acid (mass fraction 2%), and a sufficient amount of methyl tert-butyl ether was added. The organic phase was washed with water until neutral and then an excess of anhydrous sodium sulfate was added to the organic phase and allowed to stand for 12 hours. The precipitate was removed by filtration, and the filtrate was distilled off the solvent by a rotary evaporator to obtain a silicon-containing aromatic alkynyl compound (BSTEB-H) with a yield of 50.3%.

[0082] like Figure 6 As shown, FT-IR of BSTEB-H: 3291cm -1 The absorption peak of -C≡CH is 2167cm -1 A strong and sharp absorption peak of -C≡C- bond appears at 1413cm -1 and 1256cm -1 The symmetrical deformation vibration absorption peak of Si-H is 3066cm- 1 is the CH stretching vibration on the benzene ring, 1579cm -1 It is the C=C stretching vibration of the benzene ring.

[0083] like Figure 7 As shown, BSTEB-H 1 H-NMR (C2D6SO): 4.38ppm is the chemical shift of the terminal acetyl hydrogen, 7.59-7.82ppm is the chemical shift of the benzene ring hydrogen. The peak area ratio of the three is: A Si-H，Ar-H :A -C≡CH =1:1.21, which is close to the theoretical ratio of 1:1.67.

[0084] BSTEB-H is a yellow-white solid, soluble in tetrahydrofuran, methyltetrahydrofuran, toluene, acetone, N,N-dimethylformamide, dichloromethane and other solvents.

[0085] like Figure 8 As shown, the molecular weight was 476.1 as determined by time-of-flight mass spectrometry, indicating the presence of BSTEB-H in the product.

[0086] like Fig. 9 As shown, in an air atmosphere, the above silicon-containing aryl acetylene compound was cured according to the following curing process: the starting curing temperature of BSTEB-H was 143.6°C, the peak value was 151.4°C, and the end temperature was 158.9°C. BSTEB-H was cured at 140°C / 6h→170°C / 2h→180°C / 3h in sequence to obtain a dense and shiny black solid.

[0087] like Fig.10 As shown, the thermal decomposition temperature (thermal weight loss 5%) of the BSTEB-H thermally cured product in a nitrogen atmosphere is 314.3°C, and the thermal decomposition residue rate at 800°C is 72.77%.

[0088] Comparative Example 2

[0089] The silicon-containing aryl acetylene compound (TEMPS) described by the following formula:

[0090]

[0091] The synthesis method is similar to that of Example 1, except that 1,3-diethynylbenzene is used instead of 1,3,5-triethynylbenzene, and the yield is 56.3%.

[0092] like Figure 1 As shown, FT-IR of TEMPS: 3292 cm -1 The absorption peak of -C≡CH is 2155cm -1 A strong and sharp absorption peak of -C≡C- bond appears at 3064cm- 1 is the CH stretching vibration on the benzene ring, 1569cm -1 It is the stretching vibration of C=C of benzene ring. 1407cm -1 and 1256cm -1 The symmetrical deformation vibration absorption peak of Si-CH3 is 3066cm- 1 It is the stretching vibration of CH on the benzene ring.

[0093] like Figure 2 As shown, TEMPS 1 H-NMR (C2D6SO): 4.30ppm is the chemical shift of the terminal acetyl hydrogen, 746-7.69ppm is the chemical shift of the benzene ring hydrogen, and 0.71ppm is the chemical shift of the methyl hydrogen. The peak area ratio of the three is: Si-CH3 :A -C≡CH :A -Ar-H =1:1.02:4.14, which is close to the theoretical ratio of 1:1:4.

[0094] TEMPS is soluble in tetrahydrofuran, methyltetrahydrofuran, acetone, toluene, dimethylformamide, dichloromethane and other solvents.

[0095] like Figure 3 As shown, the molecular weight was 418.1 as determined by time-of-flight mass spectrometry, indicating the presence of TEMPS in the product.

[0096] like Figure 4 As shown, in an air atmosphere, the above silicon-containing aryl acetylene compound was cured according to the following curing process: the initial curing temperature of TEMPS was 189.9°C, the peak value was 202.8°C, and the end temperature was 212.5°C. After TEMPS was cured at 170°C / 4h→190°C / 2h→210°C / 2h→230°C / 3h, a dense and shiny black solid was obtained.

[0097] like Figure 5 As shown, the thermal decomposition temperature (thermal weight loss 5%) of the TEMPS thermally cured product in a nitrogen atmosphere is 684°C, and the thermal decomposition residue rate at 800°C is 93.2%.

Claims

1. A silicon-containing aryl acetylene compound, characterized in that: Its structure is shown in Formula I: Wherein, R is methyl, ethyl, vinyl or phenyl.

2. A method for preparing a silicon-containing aryl alkynyl compound according to claim 1, characterized in that: The method comprises: subjecting the compound represented by formula II to a condensation reaction with the compound represented by formula III as shown below to obtain the silicon-containing aryl alkynyl compound; Wherein, X is F, Cl, Br or I, and R is methyl, ethyl, vinyl or phenyl.

3. The method for preparing a silicon-containing aryl alkynyl compound according to claim 2, characterized in that: The compound represented by formula III is trichlorosilane.

4. The method for preparing a silicon-containing aryl alkynyl compound according to claim 3, characterized in that: The compound represented by formula III is methyltrichlorosilane, vinyltrichlorosilane or phenyltrichlorosilane.

5. The method for preparing a silicon-containing aryl alkynyl compound according to claim 2, characterized in that: The molar ratio of the compound represented by formula II to the compound represented by formula III is 3:0.99-1; And / or, the condensation reaction is carried out in a solvent, and the solvent is an anhydrous solvent; And / or, the reaction temperature of the condensation reaction is 60-70°C; And / or, the condensation reaction is carried out under the protection of nitrogen or inert gas; And / or, the specific steps of the preparation method of the silicon-containing aryl alkynyl compound include: adding a solution of the compound represented by formula III to a solution of the compound represented by formula II at room temperature to carry out the condensation reaction; And / or, the method for preparing the silicon-containing aryl alkynyl compound further comprises post-treatment.

6. The method for preparing a silicon-containing aryl acetylene compound according to claim 5, characterized in that: The solvent is at least one of an ether solvent, an amide solvent, a ketone solvent, an aromatic hydrocarbon solvent and a halogenated alkane solvent, and the solvent does not react with the compound represented by formula II; And / or, the post-treatment includes: adding acid to the reaction system to terminate the reaction, extracting, separating the liquids, washing to neutrality, removing the solvent, and obtaining the silicon-containing aryl alkynyl compound.

7. The method for preparing a silicon-containing aryl acetylene compound according to claim 6, characterized in that: The solvent is at least one of ether, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, acetone, toluene and dichloromethane.

8. The method for preparing a silicon-containing aryl alkynyl compound according to claim 2, characterized in that: The preparation method of the compound shown in formula II comprises: reacting alkyl magnesium bromide with triethynylbenzene to obtain the compound shown in formula II.

9. The method for preparing a silicon-containing aryl acetylene compound according to claim 8, characterized in that: The alkyl magnesium bromide is ethyl magnesium bromide; and / or, the molar ratio of the alkylmagnesium bromide to triethynylbenzene is 1 to 1.01:1; And / or, in the method for preparing the compound of formula II, the reaction is carried out in a solvent; the solvent is an anhydrous solvent; And / or, in the method for preparing the compound of formula II, the reaction temperature of the reaction is 60-70°C; And / or, in the method for preparing the compound of formula II, the reaction is carried out under the protection of nitrogen or inert gas; And / or, the specific steps of the preparation method of the compound represented by formula II include: under the protection of nitrogen or inert gas, triethynylbenzene, alkylmagnesium bromide and solvent are mixed and reacted.

10. The method for preparing a silicon-containing aryl alkynyl compound according to claim 9, characterized in that: The solvent is at least one of an ether solvent, an amide solvent, a ketone solvent, an aromatic hydrocarbon solvent and a halogenated alkane solvent, and the solvent does not react with alkyl magnesium bromide and the compound represented by formula II; And / or, the specific step of mixing the triethynylbenzene, alkylmagnesium bromide and solvent comprises: dropwise adding alkylmagnesium bromide solution to the mixture of triethynylbenzene and solvent under an ice-water bath.

11. The method for preparing a silicon-containing aryl alkynyl compound according to claim 10, characterized in that: The solvent is at least one of ether, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, acetone, toluene and dichloromethane.

12. A method for curing a silicon-containing aryl alkynyl compound as claimed in claim 1, characterized in that: The method comprises: curing the silicon-containing aryl acetylene compound according to claim 1 at a curing temperature of 130° C. to 190° C. to obtain a silicon-containing aryl acetylene resin.

13. The method for curing a silicon-containing aryl alkynyl compound according to claim 12, wherein: The curing is carried out in an air atmosphere; And / or, the curing temperature is 140°C-180°C; And / or, the curing time is 8-12 hours.

14. The method for curing a silicon-containing aryl alkynyl compound according to claim 13, wherein: The specific curing process includes: keeping the above silicon-containing aryl acetylene compound at 135°C-145°C for 3-7 hours, keeping it at 145°C-155°C for 1-3 hours, and keeping it at 165°C-185°C for 2-6 hours.

15. The method for curing a silicon-containing aryl alkynyl compound according to claim 14, wherein: The specific process of the curing includes: keeping the above-mentioned silicon-containing aryl alkynyl compound at 135°C-145°C for 3-5 hours, keeping it at 145°C-155°C for 1-3 hours, keeping it at 165°C-175°C for 1-3 hours, and keeping it at 175°C-185°C for 2-4 hours; or, keeping the above-mentioned silicon-containing aryl alkynyl compound at 135°C-145°C for 5-7 hours, keeping it at 145°C-155°C for 1-3 hours, and keeping it at 175°C-185°C for 2-4 hours.

16. A silicon-containing arylacetylene resin, which is obtained by the curing method of the silicon-containing arylacetylene compound according to any one of claims 12 to 15.

17. A silicon-containing arylacetylene resin, which is obtained by polymerizing and cross-linking the silicon-containing arylacetylene compound according to claim 1 or 2, wherein: The 5% thermal weight loss temperature of the silicon-containing aromatic acetylene resin in a nitrogen atmosphere is 780° C.-849° C.

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