阅读说明：本技术 含硅芳炔基化合物、其制备和固化方法及含硅芳炔树脂 (Silicon-containing aryne-based compound, preparation and curing method thereof and silicon-containing aryne resin ) 是由 蔡春华 鲁越 黄思敏 王立权 林嘉平 于 2021-10-14 设计创作，主要内容包括：本发明提供了一种含硅芳炔基化合物、其制备和固化方法及含硅芳炔树脂。所述的含硅芳炔基化合物,其结构如式I所示,其固化温度低、且固化产物具有高耐热性。(The invention provides a silicon-containing aryne-based compound, a preparation method and a curing method thereof, and silicon-containing aryne resin. The structure of the silicon-containing aryne-based compound is shown as a formula I, the curing temperature is low, and the cured product has high heat resistance.)

1. A silicon-containing aryne-based compound is characterized in that the structure is shown as formula I:

wherein R is methyl, ethyl, vinyl or phenyl.

2. A method for producing a silicon-containing arylalkynyl compound according to claim 1, comprising: carrying out condensation reaction on a compound shown as a formula II and a compound shown as a formula III as shown in the specification to obtain the silicon-containing aryne-based 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 arylalkynyl compound according to claim 2, wherein the compound represented by the formula III is trichlorosilane, such as methyltrichlorosilane, vinyltrichlorosilane or phenyltrichlorosilane.

4. The method for preparing a silicon-containing arylalkynyl compound according to claim 2, wherein the molar ratio of the compound represented by the formula II to the compound represented by the formula III is 3: 0.99 to 1;

and/or, the condensation reaction is carried out in a solvent, and the solvent is an anhydrous solvent; preferably, 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 shown in the formula II; more preferably, the solvent is at least one of diethyl ether, tetrahydrofuran, methyltetrahydrofuran, N-dimethylformamide, acetone, toluene and dichloromethane;

and/or the reaction temperature of the condensation reaction is 60-70 ℃;

and/or, the condensation reaction is carried out under the protection of nitrogen or inert gas;

and/or, the preparation method of the silicon-containing aryne alkynyl compound comprises the following specific steps: adding a solution of a compound shown in a formula III into a solution of a compound shown in a formula II at room temperature or below to perform the condensation reaction;

and/or, the preparation method of the silicon-containing aryne-base compound also comprises post-treatment; preferably, the post-processing comprises: adding acid into the reaction system to terminate the reaction, extracting, separating liquid, washing to be neutral, and removing the solvent to obtain the silicon-containing aryne-based compound.

5. The method for preparing a silicon-containing arynyl compound according to claim 2, wherein the method for preparing the compound represented by the formula II comprises: and (3) reacting alkyl magnesium bromide with triethynyl benzene to obtain the compound shown in the formula II.

6. The method according to claim 5, wherein said alkyl magnesium bromide is ethyl magnesium bromide;

and/or the molar ratio of the alkyl magnesium bromide to the triethynyl benzene is 1-1.01: 1;

and/or, in the preparation method of the compound shown in the formula II, the reaction is carried out in a solvent; the solvent is an anhydrous solvent; preferably, 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 shown in the formula II; more preferably, the solvent is at least one of diethyl ether, tetrahydrofuran, methyltetrahydrofuran, N-dimethylformamide, acetone, toluene and dichloromethane;

and/or in the preparation method of the compound shown in the formula II, the reaction temperature of the reaction is 60-70 ℃;

and/or in the preparation method of the compound shown in the formula II, the reaction is carried out under the protection of nitrogen or inert gas;

and/or the preparation method of the compound shown in the formula II comprises the following specific steps: mixing triethylalkynyl benzene, alkyl magnesium bromide and a solvent under the protection of nitrogen or inert gas, and then reacting; preferably, the specific steps of mixing the triethylalkynyl benzene and the alkyl magnesium bromide with the solvent comprise: and dropwise adding an alkyl magnesium bromide solution into the mixture of the triethynylbenzene and the solvent in an ice water bath.

7. A method of curing a silicon-containing arylalkynyl compound according to claim 1, comprising: curing the silicon-containing aryne-based compound according to claim 1 at a curing temperature of 130 ℃ to 190 ℃ to obtain the silicon-containing aryne resin.

8. The method for curing a silicon-containing arylalkynyl compound according to claim 7, wherein the curing is performed in an air atmosphere;

and/or the curing temperature is 140-180 ℃; more preferably, the specific process of curing comprises: keeping the silicon-containing aryne-based compound at 135-145 ℃ for 3-7 hours, at 145-155 ℃ for 1-3 hours and at 165-185 ℃ for 2-6 hours in sequence; further preferably, the specific process of curing includes: keeping the silicon-containing aryne-based compound at 135-145 ℃ for 3-5 hours, at 145-155 ℃ for 1-3 hours, at 165-175 ℃ for 1-3 hours and at 175-185 ℃ for 2-4 hours in sequence; or, the silicon-containing aryne-based compound is kept for 5 to 7 hours at 135 to 145 ℃, 1 to 3 hours at 145 to 155 ℃ and 2 to 4 hours at 175 to 185 ℃ in turn;

and/or the curing time is 8-12 hours.

9. A silicon-containing aryne resin produced by the method for curing a silicon-containing aryne-based compound according to claim 7 or 8.

10. A silicon-containing aryne resin obtained by polymerizing and crosslinking the silicon-containing aryne compound according to claim 1 or 2, wherein the 5% thermal weight loss temperature of the silicon-containing aryne resin in a nitrogen atmosphere is 780 ℃ to 849 ℃.

Technical Field

The invention relates to a silicon-containing aryne-base compound, a preparation method and a curing method thereof, and silicon-containing aryne resin.

Background

The silicon-containing aryne resin is organic-inorganic hybrid novel aryne resin formed by introducing inorganic silicon elements into a main chain structure of an organic aryne polymer. The resin has excellent heat resistance and high-temperature ceramic property, and is expected to be used as a high-temperature-resistant polymer matrix in the field of aerospace. Nowadays, the main silicon-containing aryne polymers still take linear molecules as the main part and form a cross-linked three-dimensional network structure after thermal curing. However, the presence of internal alkynyl groups in silicon-containing aryne polymers tends to result in higher curing temperatures required, with peak curing temperatures around 210 ℃. And due to the influence of a linear structure, a large amount of internal alkynyl groups in the material cannot be fully reacted, and the crosslinking density is low, so that the thermal property of the material cannot be fully exerted.

The branched molecular structure has a large number of functional groups at the end, and compared with the linear structure molecule, the polymer has lower viscosity and good solubility. A large number of functional groups at the tail end of the branched molecular structure can be subjected to full curing reaction, and a three-dimensional network structure with high crosslinking density is formed, so that the heat resistance of the branched molecular structure is improved. Three novel branched structure silicon-containing arylalkynyl resins are described by Dai et al in the Journal of Polymer Engineering, vol.40, No.8,2020, pp.676-684, with a cure temperature in the range of 140-_5％The highest temperature can reach 697 ℃, and the resin has low viscosity, and compared with linear silicon-containing aryne-based resin, the heat resistance is greatly improved.

Therefore, the method has great significance for researching the branched silicon-containing aryne polymer.

Disclosure of Invention

It is a first object of the present invention to provide a compound which has a low curing temperature and a cured product having high heat resistance.

The second object of the present invention is to provide a process for producing the above compound.

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

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a silicon-containing aryne-based compound, which has a structure shown in a formula I:

wherein R is methyl, ethyl, vinyl or phenyl.

The invention also provides a preparation method of the silicon-containing aryne-based compound, which comprises the following steps: carrying out condensation reaction on a compound shown as a formula II and a compound shown as a formula III to obtain the silicon-containing aryne-based compound;

wherein, X is F, Cl, Br or I, and R is methyl, ethyl, vinyl or phenyl.

Among them, the compound represented by the formula III is preferably trichlorosilane, such as methyltrichlorosilane, vinyltrichlorosilane or phenyltrichlorosilane.

Wherein, the compound shown in the formula II can be used in the conventional amount in the condensation reaction in the field. For example, the molar ratio of the compound of formula II to the compound of formula III may be 3: 0.99 to 1.

Wherein the condensation reaction may be carried out in a solvent. The solvent may be an anhydrous solvent. The solvent may be at least one of an ether-based solvent (e.g., at least one of diethyl ether, tetrahydrofuran, and methyltetrahydrofuran), an amide-based solvent (e.g., N-dimethylformamide, etc.), a ketone-based solvent (e.g., acetone, etc.), an aromatic-based solvent (e.g., toluene, etc.), and a haloalkane-based solvent (e.g., dichloromethane, etc.), which does not react with the compound represented by formula II.

Wherein the reaction conditions of the condensation reaction may be conventional in the art. For example, the condensation reaction may be carried out at a reaction temperature of 60 to 70 ℃. For example, the condensation reaction may be carried out for a reaction time of 2 to 4 hours. For example, the reaction may be carried out under nitrogen or inert gas.

The preparation method of the silicon-containing arylalkynyl compound comprises the following specific steps: the condensation reaction is carried out by adding a solution of a compound represented by the formula III to a solution of a compound represented by the formula II at room temperature or below. The reaction temperature is set to be 10 ℃ to 15 ℃ below room temperature, for example, and the main purpose of setting the reaction temperature below room temperature is to prevent direct rapid reaction after the addition of the compound of formula III, and the temperature is lowered to slow down the reaction rate during the dropwise addition.

The preparation method of the silicon-containing aryne-based compound also comprises post-treatment. The post-processing may include: the reaction system is added with acid to stop the reaction, and the reaction is extracted (for example, with methyl tert-butyl ether or dichloromethane), separated, washed (for example, with deionized water) to neutrality, and the solvent is removed (for example, by distillation under reduced pressure) to obtain the silicon-containing arynyl compound.

In the invention, the preparation method of the compound shown in the formula II comprises the following steps: and (3) reacting alkyl magnesium bromide with triethynyl benzene to obtain the compound shown in the formula II.

Wherein, the alkyl magnesium bromide can be ethyl magnesium bromide and the like. The reaction of ethylmagnesium bromide with triethynylbenzene is shown below:

wherein, the alkyl magnesium bromide can be used in the conventional amount in the reaction in the field. For example, the molar ratio of the alkyl magnesium bromide to the triethynyl benzene can be 1 to 1.01:1, such as 1:1.

Wherein the reaction may be carried out in a solvent. The solvent may be an anhydrous solvent. The solvent may be at least one of an ether-based solvent (e.g., at least one of diethyl ether, tetrahydrofuran, and methyltetrahydrofuran), an amide-based solvent (e.g., N-dimethylformamide, etc.), a ketone-based solvent (e.g., acetone, etc.), an aromatic-based solvent (e.g., toluene, etc.), and a haloalkane-based solvent (e.g., dichloromethane, etc.), which does not react with the alkyl magnesium bromide and the compound of formula II.

Wherein the reaction conditions of the reaction may be conventional in the art for such reactions. For example, the reaction temperature of the reaction may be 60 to 70 ℃. For example, the reaction time of the reaction may be 2 to 4 hours. For example, the reaction may be carried out under nitrogen or inert gas.

The preparation method of the compound shown in the formula II comprises the following specific steps: mixing the triethynyl benzene, the alkyl magnesium bromide and the solvent for reaction under the protection of nitrogen or inert gas. The specific steps of mixing the triethynyl phenylalkyl magnesium bromide and the solvent can comprise: and dropwise adding an alkyl magnesium bromide solution into the mixture of the triethynylbenzene and the solvent in an ice water bath.

Wherein, after the reaction, the obtained compound shown in the formula II and the compound shown in the formula III can be directly subjected to condensation reaction without post-treatment.

The preparation method of the silicon-containing arylalkynyl compound comprises the following specific steps: mixing triethylalkynyl benzene and an anhydrous solvent, adding the mixture into a reaction container protected by nitrogen or inert gas, dropwise adding an ethyl magnesium bromide solution into the reaction system in an ice water bath, heating after dropwise adding, and carrying out heat preservation reaction at 60-70 ℃ for 2-4 hours; cooling the reaction system to room temperature, dropwise adding trichlorosilane into the system, heating to 60-70 ℃ after dropwise adding, continuing to react for 2-4 hours, then adding acid into the system to terminate the reaction, fully stirring, extracting with methyl tert-butyl ether or dichloromethane, separating liquid, washing with deionized water to be neutral, and removing the solvent by reduced pressure distillation to obtain the silicon-containing aryne compound.

The invention also provides a curing method of the silicon-containing aryne-based compound, which is characterized by comprising the following steps: and curing the silicon-containing aryne-based compound at the curing temperature of 130-190 ℃ to obtain the silicon-containing aryne resin.

Wherein the curing may be performed in an air atmosphere.

Preferably, the curing temperature is 140-180 ℃. More preferably, the specific process of curing comprises: the silicon-containing aryne-based compound is kept for 3 to 7 hours at 135 to 145 ℃, 1 to 3 hours at 145 to 155 ℃ and 2 to 6 hours at 165 to 185 ℃ in turn. Further, the specific process of curing includes: keeping the silicon-containing aryne-based compound at 135-145 ℃ for 3-5 hours, at 145-155 ℃ for 1-3 hours, at 165-175 ℃ for 1-3 hours and at 175-185 ℃ for 2-4 hours in sequence; or, the silicon-containing aryne-based compound is kept for 5 to 7 hours at 135 to 145 ℃, 1 to 3 hours at 145 to 155 ℃ and 2 to 4 hours at 175 to 185 ℃ in turn.

Wherein the curing time may be 8 to 12 hours.

Wherein, in the curing process, the silicon-containing aryne-base compound is polymerized and crosslinked.

The invention also provides silicon-containing aryne resin which is prepared from the silicon-containing aryne-base compound by the curing method.

Wherein, the 5 percent thermal weight loss temperature of the silicon-containing aryne resin in the nitrogen atmosphere can be 780-849 ℃.

The invention also provides silicon-containing aryne resin which is obtained by polymerizing and crosslinking the silicon-containing aryne compound, wherein the 5% thermal weight loss temperature of the silicon-containing aryne resin in a nitrogen atmosphere is 780-849 ℃.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows:

the silicon-containing aryne-based compound can be dissolved in a plurality of common organic solvents, such as tetrahydrofuran, methyltetrahydrofuran, toluene, acetone, methyl tert-butyl ether, dichloromethane, N-dimethylformamide and the like, and has excellent process performance. The high-temperature-resistant resin can be thermally polymerized, crosslinked and cured at a lower temperature to form a compact cured product, no small molecules are emitted during curing, the cured product has a highly crosslinked three-dimensional network structure and excellent thermal stability, can be used for preparing high-temperature-resistant resin and advanced resin matrix composite materials, and has a great development prospect in the field of aerospace.

Drawings

FIG. 1 is an infrared spectrum (FT-IR) of a silicon-containing arylalkynyl compound (BSTEB) and a comparative TEMPS;

FIG. 2 is a graph of silicon-containing arylalkynyl compound (BSTEB) and comparative TEMPS¹H-NMR nuclear magnetic map;

FIG. 3 is a MALDI-TOF-MS mass spectrum of a silicon-containing arylalkynyl compound (BSTEB) and a reference TEMPS;

FIG. 4 is a DSC of silicon-containing arylalkynyl compounds (BSTEB) and a comparative TEMPS;

FIG. 5 is a TGA plot under nitrogen atmosphere of a thermal cure product of a silicon-containing arylalkynyl compound (BSTEB) and a comparative TEMPS.

FIG. 6 is an infrared spectrum (FT-IR) of a silicon-containing arylalkynyl compound (BSTEB-H);

FIG. 7 is a scheme showing the preparation of silicon-containing aralkynyl compounds (BSTEB-H)¹H-NMR nuclear magnetic map;

FIG. 8 is a MALDI-TOF-MS mass spectrum of a silicon-containing arylalkynyl compound (BSTEB-H);

FIG. 9 is a DSC of a silicon-containing arylalkynyl compound (BSTEB-H);

FIG. 10 is a TGA graph of a thermal cured product of a silicon-containing arylalkynyl compound (BSTEB-H) under nitrogen.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

In the invention, the structure of the silicon-containing aromatic alkynyl compound is characterized by infrared spectrum and nuclear magnetic resonance hydrogen spectrum (taking deuterated DMSO as a solvent), and the molecular weight is measured by a time-of-flight mass spectrometer (MALDI-TOF-MS) method; the curing temperature interval of the silicon-containing aryne base compound is measured by adopting Differential Scanning Calorimetry (DSC), and is measured in N₂The atmosphere was tested at a temperature rise rate of 5 ℃/min. 5% Heat weight loss temperature (Td) of the cured product thereof_5％) The method is characterized by using a thermal weight loss analyzer for testing, wherein the temperature rise rate is 10 ℃/min under a nitrogen atmosphere.

Example 1

In a 500mL three-neck flask equipped with a nitrogen conduit, a dropper and a condenser, dehumidification and oxygen removal were performed by evacuation and replacement with nitrogen gas several times. 4.505g (0.03mol) of 1,3, 5-triethynyl benzene is dissolved in 50mL of anhydrous tetrahydrofuran and added into a three-neck flask under the protection of nitrogen, 30.3mL of ethyl magnesium bromide/tetrahydrofuran solution (ethyl magnesium bromide is dissolved in anhydrous tetrahydrofuran, the concentration of the ethyl magnesium bromide is 1mol/L) is added dropwise in an ice-water bath environment, and the reaction is carried out for 2 hours at 68 ℃ after the dropwise addition. After the reaction was completed, the reaction system was cooled to room temperature or lower, and trichloromethylsilane/tetrahydrofuran solution (1.495g of 0.01mol of trichloromethylsilane dissolved in 20mL of anhydrous tetrahydrofuran) was added thereto to conduct condensation reaction at 68 ℃ for 2 hours with heat preservation. Terminating the reaction by using 50mL of dilute hydrochloric acid (the mass fraction is 2%), adding sufficient methyl tert-butyl ether, washing the mixture to be neutral by using water, taking an organic phase, adding excessive anhydrous sodium sulfate into the organic phase, standing the mixture for 12 hours, filtering the mixture to remove precipitates, and distilling the filtrate by using a rotary evaporator to remove a solvent to obtain the silicon-containing aryne-based compound (BSTEB-M) with the structure shown in the formula I, wherein R is methyl, and the yield is 51.6%.

As shown in FIG. 1, the FT-IR of BSTEB-M: 3382cm^-1Is an absorption peak of-C ≡ C-H, 2166cm^-1The absorption peak with strong and sharp-C-bond appears at 2965cm^-1Is CH₃Middle C-H stretching vibration absorption peak, 1413cm^-1And 1256cm^-1Is of Si-CH₃Symmetrical deformation vibration absorption peak 3066cm-¹Is C-H stretching vibration on benzene ring, 1578cm^-1The benzene ring C is stretched and vibrated.

As shown in FIG. 2, of BSTEB-M¹H-NMR(C₂D₆SO): 4.38ppm is the chemical shift of terminal alkynyl hydrogen, 7.59-7.82 ppm 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 as follows: a. the_Si-CH3:A_-C≡CH:A_-Ar-H1:1.93:2.96, closer to the theoretical ratio of 1:2: 3.

BSTEB-M is a brown yellow solid, and can be dissolved in solvents such as tetrahydrofuran, methyltetrahydrofuran, toluene, acetone, N-dimethylformamide, dichloromethane and the like.

As shown in FIG. 3, the molecular weight was 490.1 by time-of-flight mass spectrometry, and BSTEB-M was present in the product.

As shown in FIG. 4, the above-mentioned silicon-containing aralkynyl compound is cured in an air atmosphere according to the following curing procedure: BSTEB-M has an initial cure temperature of 146.2 deg.C, a peak of 156.7 deg.C, and an end temperature of 174.1 deg.C. BSTEB-M is cured sequentially at 140 ℃/4h → 150 ℃/2h → 170 ℃/2h → 180 ℃/3h to obtain compact and bright black solid.

As shown in FIG. 5, the thermal decomposition temperature (5% loss on heat) of the BSTEB-M thermoset product in a nitrogen atmosphere was 778 ℃ and the pyrolysis residual rate at 800 ℃ was 94.7%.

Example 2

In a 500mL three-neck flask equipped with a nitrogen conduit, a dropper and a condenser, dehumidification and oxygen removal were performed by evacuation and replacement with nitrogen gas several times. 4.505g (0.03mol) of 1,3, 5-triethynyl benzene is dissolved in 50mL of anhydrous tetrahydrofuran and added into a three-neck flask under the protection of nitrogen, 30.3mL of ethyl magnesium bromide/tetrahydrofuran solution (ethyl magnesium bromide is dissolved in anhydrous tetrahydrofuran, the concentration of the ethyl magnesium bromide is 1mol/L) is added dropwise in an ice-water bath environment, and the reaction is carried out for 2 hours at 68 ℃ after the dropwise addition. After completion of the reaction, the reaction system was cooled to room temperature or lower, and a trichlorophenylsilane/tetrahydrofuran solution (2.115g of 0.01mol of trichlorophenylsilane dissolved in 20mL of anhydrous tetrahydrofuran) was added thereto to conduct condensation reaction at 68 ℃ for 2 hours with heat preservation. Terminating the reaction by using 50mL of dilute hydrochloric acid (the mass fraction is 2%), adding sufficient methyl tert-butyl ether, washing the mixture to be neutral by using water, taking an organic phase, adding excessive anhydrous sodium sulfate into the organic phase, standing the mixture for 12 hours, filtering the mixture to remove precipitates, and distilling the filtrate by using a rotary evaporator to remove a solvent to obtain the silicon-containing aryne-based compound (BSTEB-B) with the structure shown in the formula I, wherein R is phenyl and the yield is 50.7%.

As shown in FIG. 1, the FT-IR of BSTEB-B: 3290cm^-1Is an absorption peak of-C ≡ C-H, 2165cm^-1A strong and sharp absorption peak of-C ≡ C-bond appears at the position, 3069cm-¹Is C-H stretching vibration on benzene ring, 1578cm^-1The benzene ring C is stretched and vibrated.

As shown in FIG. 2, of BSTEB-B¹H-NMR(C₂D₆SO): 4.38ppm are terminal alkynesChemical shift of radical hydrogen, 7.59-7.82 ppm is chemical shift of benzene ring hydrogen. The peak area ratio of the two is as follows: a. the_-C≡CH:A_-Ar-H1:2.63, which is closer to the theoretical ratio of 1: 2.33.

BSTEB-B is a brown yellow solid, and can be dissolved in solvents such as tetrahydrofuran, methyltetrahydrofuran, acetone, toluene, dimethylformamide, dichloromethane and the like.

As shown in FIG. 3, the molecular weight was 552.13 as measured by time-of-flight mass spectrometry, and BSTEB-B was present in the product.

As shown in FIG. 4, the above-mentioned silicon-containing aralkynyl compound is cured in an air atmosphere according to the following curing procedure: BSTEB-B has an initial cure temperature of 148.2 deg.C, a peak of 158.1 deg.C, and an end temperature of 174.0 deg.C. BSTEB-B is cured sequentially at 140 ℃/4h → 150 ℃/2h → 170 ℃/2h → 180 ℃/3h to obtain compact and bright black solid.

As shown in FIG. 5, the thermal decomposition temperature (5% loss on heat) of the BSTEB-B thermoset product in a nitrogen atmosphere was 804 ℃ and the pyrolysis residual rate at 800 ℃ was 95.0%.

Example 3

In a 500mL three-neck flask equipped with a nitrogen conduit, a dropper and a condenser, dehumidification and oxygen removal were performed by evacuation and replacement with nitrogen gas several times. 4.505g (0.03mol) of 1,3, 5-triethynyl benzene is dissolved in 50mL of anhydrous tetrahydrofuran and added into a three-neck flask under the protection of nitrogen, 30.3mL of ethyl magnesium bromide/tetrahydrofuran solution (ethyl magnesium bromide is dissolved in anhydrous tetrahydrofuran, the concentration of the ethyl magnesium bromide is 1mol/L) is added dropwise in an ice-water bath environment, and the reaction is carried out for 2 hours at 68 ℃ after the dropwise addition. After the reaction was completed, the reaction system was cooled to room temperature or lower, and a solution of trichloroethylsilane/tetrahydrofuran (1.615g of 0.01mol of trichloroethylsilane dissolved in 20mL of anhydrous tetrahydrofuran) was added thereto to conduct condensation reaction at 68 ℃ for 2 hours. Terminating the reaction by using 50mL of dilute hydrochloric acid (the mass fraction is 2%), adding sufficient methyl tert-butyl ether, washing the mixture to be neutral by using water, taking an organic phase, adding excessive anhydrous sodium sulfate into the organic phase, standing the mixture for 12 hours, filtering the mixture to remove precipitates, and distilling the filtrate by using a rotary evaporator to remove a solvent to obtain the silicon-containing aryne-based compound (BSTEB-V) with the structure shown in the formula I, wherein R is vinyl and the yield is 60%.

As shown in FIG. 1, the FT-IR of BSTEB-V: 3290cm^-1Is an absorption peak of-C ≡ C-H, 2166cm^-1A strong and sharp absorption peak of-C ≡ C-bond appears at the position, 3064cm-¹Is C-H stretching vibration on benzene ring, 3015cm^-1is-CH ═ CH₂Upper hydrogen vibration peak, 1579cm^-1Is the benzene ring C ═ C stretching vibration peak.

As shown in FIG. 2, of BSTEB-V¹H-NMR(C₂D₆SO): 4.38ppm is the chemical shift value of terminal alkynyl hydrogen, 7.59-7.82 ppm is the chemical shift value of benzene ring hydrogen, and 6.1-6.4ppm is the chemical shift value of vinyl. The peak area ratio of the three is as follows: a. the_-CH＝CH2:A_-C≡CH:A_-Ar-H1:1.95:3.01, closer to the theoretical ratio of 1:2: 3.

BSTEB-V is a brown yellow solid, and can be dissolved in solvents such as tetrahydrofuran, methyltetrahydrofuran, acetone, toluene, dimethylformamide, dichloromethane and the like.

As shown in FIG. 3, the molecular weight was 502.12 as measured by time-of-flight mass spectrometry, and BSTEB-V was present in the product.

As shown in FIG. 4, the above-mentioned silicon-containing aralkynyl compound is cured in an air atmosphere according to the following curing procedure: BSTEB-V has an initial cure temperature of 143.7 deg.C, a peak of 154.4 deg.C, and an end temperature of 170.2 deg.C. BSTEB-V is cured under the conditions of 140 ℃/6h → 150 ℃/2h → 180 ℃/3h in sequence to obtain a dense and bright black solid.

As shown in FIG. 5, the thermal decomposition temperature (5% loss on heat) of the BSTEB-V thermoset product in a nitrogen atmosphere was 849 ℃, and the pyrolysis residual rate at 800 ℃ was 96.2%.

Comparative example 1

A silicon-containing arylalkynyl compound (BSTEB-H) described by the following formula:

the synthesis method comprises the following steps:

in a 500mL three-neck flask equipped with a nitrogen conduit, a dropper and a condenser, dehumidification and oxygen removal were performed by evacuation and replacement with nitrogen gas several times. 4.505g (0.03mol) of 1,3, 5-triethynyl benzene is dissolved in 50mL of anhydrous tetrahydrofuran and added into a three-neck flask under the protection of nitrogen, 30.3mL of ethyl magnesium bromide/tetrahydrofuran solution (ethyl magnesium bromide is dissolved in anhydrous tetrahydrofuran, the concentration of the ethyl magnesium bromide is 1mol/L) is added dropwise in an ice-water bath environment, and the reaction is carried out for 2 hours at 68 ℃ after the dropwise addition. After the reaction was completed, the reaction system was cooled to room temperature or lower, and a trichlorosilane/tetrahydrofuran solution (1.354g of 0.01mol of trichlorosilane dissolved in 20mL of anhydrous tetrahydrofuran) was added thereto to conduct condensation reaction for 2 hours at 68 ℃ with heat preservation. The reaction was terminated with 50mL of dilute hydrochloric acid (mass fraction: 2%), sufficient methyl t-butyl ether was added, the mixture was washed with water to neutrality, the organic phase was taken out, excess 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 with a rotary evaporator to obtain a silicon-containing arylalkynyl compound (BSTEB-H) with a yield of 50.3%.

As shown in FIG. 6, the FT-IR of BSTEB-H: 3291cm^-1Is an absorption peak of-C ≡ C-H, 2167cm^-1A strong and sharp absorption peak of-C ≡ C-bond, 1413cm^-1And 1256cm^-1Is a symmetric deformation vibration absorption peak of Si-H, 3066cm-¹Is C-H stretching vibration on benzene ring, 1579cm^-1The benzene ring C is stretched and vibrated.

As shown in FIG. 7, of BSTEB-H¹H-NMR(C₂D₆SO): 4.38ppm is the chemical shift of terminal alkynyl hydrogen, 7.59-7.82 ppm 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 as follows: a. the_Si-H，Ar-H:A_-C≡CH1:1.21, which is closer to the theoretical ratio of 1: 1.67.

BSTEB-H is a yellow white solid which can be dissolved in solvents such as tetrahydrofuran, methyltetrahydrofuran, toluene, acetone, N-dimethylformamide, dichloromethane and the like.

As shown in FIG. 8, the molecular weight was 476.1 as measured by time-of-flight mass spectrometry, and BSTEB-H was present in the product.

As shown in FIG. 9, the above-mentioned silicon-containing aralkynyl group-containing compound is cured in an air atmosphere according to the following curing procedure: BSTEB-H has an initial cure temperature of 143.6 deg.C, a peak at 151.4 deg.C, and an end temperature of 158.9 deg.C. BSTEB-H is cured under the conditions of 140 ℃/6H → 170 ℃/2H → 180 ℃/3H in sequence to obtain compact and bright black solid.

As shown in FIG. 10, the thermal decomposition temperature (5% loss on heat) of the BSTEB-H thermoset product in a nitrogen atmosphere was 314.3 ℃ and the pyrolysis residue rate at 800 ℃ was 72.77%.

Comparative example 2

A silicon-containing arylalkynyl compound (TEMPS) described by the following formula:

the synthesis was similar to example 1, except that 1, 3-diethynylbenzene was used instead of 1,3, 5-triethynylbenzene, and the yield was 56.3%.

As shown in FIG. 1, FT-IR of TEMPS: 3292cm^-1Is an absorption peak of-C.ident.C-H, 2155cm^-1A strong and sharp absorption peak of-C ≡ C-bond appears at the position, 3064cm-¹1569cm for C-H stretching vibration on benzene ring^-1The benzene ring C is stretched and vibrated. 1407cm^-1And 1256cm^-1Is of Si-CH₃Symmetrical deformation vibration absorption peak 3066cm-¹C-H stretching vibration on a benzene ring.

As shown in FIG. 2, of TEMPS¹H-NMR(C₂D₆SO): 4.30ppm is the chemical shift of terminal alkynyl hydrogen, 746-7.69 ppm is the chemical shift of benzene ring hydrogen, and 0.71ppm is the chemical shift of methyl hydrogen. The peak area ratio of the three is as follows: a. the_Si-CH3:A_-C≡CH:A_-Ar-H1:1.02:4.14, which is closer to the theoretical ratio of 1:1: 4.

TEMPS is soluble in solvents such as tetrahydrofuran, methyltetrahydrofuran, acetone, toluene, dimethylformamide, dichloromethane, and the like.

As shown in fig. 3, the molecular weight was 418.1 by time-of-flight mass spectrometry, with TEMPS present in the product.

As shown in FIG. 4, the above-mentioned silicon-containing aralkynyl compound is cured in an air atmosphere according to the following curing procedure: TEMPS has an onset of cure temperature of 189.9 deg.C, a peak of 202.8 deg.C and an end temperature of 212.5 deg.C. And the TEMPS is cured under the conditions of 170 ℃/4h → 190 ℃/2h → 210 ℃/2h → 230 ℃/3h in sequence to obtain the dense and bright black solid.

As shown in FIG. 5, the thermal decomposition temperature (5% loss on heat) of the TEMPS thermal cured product in a nitrogen atmosphere was 684 ℃ and the pyrolysis residue ratio at 800 ℃ was 93.2%.