阅读说明：本技术 一种含苯乙炔基的笼型聚倍半硅氧烷及其合成方法与应用 (Phenylethynyl-containing cage type polysilsesquioxane and synthetic method and application thereof ) 是由 王振合 张春波 袁航 谢非 张昊 于 2021-06-23 设计创作，主要内容包括：本发明提供了一种含苯乙炔基的笼型聚倍半硅氧烷及其合成方法与应用。所述笼型聚倍半硅氧烷具有如(Ⅰ)所示结构：,其中R基团为A基团为所述方法包括：将4-苯乙炔基苯酐、N-[(七异丁基POSS)丙基]-3,5-二氨基苯甲酰胺加入到有机溶剂中进行反应,然后减压蒸馏,再在醇类溶剂中加热回流除去未反应的4-苯乙炔基苯酐,得到所述含苯乙炔基的笼型聚倍半硅氧烷。本发明还提供了所述含苯乙炔基的笼型聚倍半硅氧烷在制备热固性高分子聚合物中的应用。本发明所述含苯乙炔基的笼型聚倍半硅氧烷可以通过加热直接交联成具有耐高温、耐原子氧和低介电特性的热固性高分子聚合物。(The invention provides a polyhedral oligomeric silsesquioxane containing phenylethynyl and a synthesis method and application thereof. The cage type polysilsesquioxane has a structure as shown in (I): wherein R is a group A radical is The method comprises the following steps: 4-phenylethynyl phthalic anhydride, N- [ (heptaisobutyl POSS) propyl group]Adding 3, 5-diaminobenzamide into an organic solvent for reaction, then distilling under reduced pressure, and heating and refluxing in an alcohol solvent to remove unreacted 4-phenylethynyl phthalic anhydride to obtain the compoundThe polyhedral oligomeric silsesquioxane containing phenylethynyl is described. The invention also provides application of the polyhedral oligomeric silsesquioxane containing phenylethynyl in preparation of thermosetting high-molecular polymers. The polyhedral oligomeric silsesquioxane containing phenylethynyl can be directly crosslinked into a thermosetting high polymer with high temperature resistance, atomic oxygen resistance and low dielectric property by heating.)

1. The polyhedral oligomeric silsesquioxane containing phenylethynyl is characterized in that the polyhedral oligomeric silsesquioxane containing phenylethynyl is a compound with a structure shown as (I):

wherein the structural formula of the R group is

The structural formula of the A group is

2. The method for synthesizing the phenylethynyl-containing polyhedral oligomeric silsesquioxane of claim 1, wherein the method for synthesizing the phenylethynyl-containing polyhedral oligomeric silsesquioxane comprises the following steps:

(1) adding 4-phenylethynyl phthalic anhydride with the A group, N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide and an organic solvent into a reactor for reaction to obtain a mixed solution containing the phenylethynyl-containing polyhedral oligomeric silsesquioxane;

(2) carrying out post-treatment on the mixed solution obtained in the step (1) to obtain the polyhedral oligomeric silsesquioxane containing phenylethynyl;

wherein the structural formula of the N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide is shown as the formula (II):

3. the method of synthesis according to claim 2, characterized in that:

in the step (1), the reaction is carried out for 6-12h under the protection of nitrogen and heating reflux reaction in an oil bath.

4. The method of synthesis according to claim 2, characterized in that:

the molar mass ratio of the 4-phenylethynyl phthalic anhydride to the N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide is (2.2-5): 1; and/or

The ratio of the mass of the organic solvent to the sum of the mass of the 4-phenylethynyl phthalic anhydride and the mass of the N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide is (4-8): 1.

5. The method of synthesis according to claim 2, characterized in that:

the organic solvent is at least one of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, m-cresol and dimethyl sulfoxide.

6. The method of synthesis according to claim 2, characterized in that:

in step (2), the post-processing comprises the following sub-steps:

(i) carrying out reduced pressure distillation on the mixed solution obtained in the step (1) to obtain a concentrated solution;

(ii) and adding the concentrated solution into an alcohol solvent, heating and refluxing for 4-8h, cooling, separating, cleaning and drying in vacuum to obtain the polyhedral oligomeric silsesquioxane containing phenylethynyl.

7. The method of synthesis according to claim 6, characterized in that:

the mass ratio of the mixed solution to the concentrated solution is (3-7) to 1;

the mass ratio of the alcohol solvent to the concentrated solution is (2-6) to 1; and/or

The alcohol solvent is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and ethylene glycol monomethyl ether.

8. The method of synthesis according to claim 6, characterized in that:

the drying temperature of the vacuum drying is 80-150 ℃, and the drying time is 8-24 h.

9. Use of the phenylethynyl-containing polyhedral oligomeric silsesquioxane as defined in claim 1 or the phenylethynyl-containing polyhedral oligomeric silsesquioxane obtained by the synthesis method as defined in any one of claims 2 to 8 in preparation of a thermosetting high polymer, wherein the phenylethynyl-containing polyhedral oligomeric silsesquioxane is obtained by heating the phenylethynyl-containing polyhedral oligomeric silsesquioxane for a crosslinking reaction.

10. Use according to claim 9, characterized in that:

the reaction temperature of the crosslinking reaction is 330-400 ℃, and the reaction time is 1-6 h.

Technical Field

The invention relates to the technical field of polysilsesquioxane synthesis, in particular to polyhedral oligomeric silsesquioxane containing phenylethynyl and a synthesis method and application thereof.

Background

Cage Polysilsesquioxane (POSS) is a cage compound formed by connecting silicon oxygen bonds, the excellent atomic oxygen resistance and high temperature resistance are endowed by rich silicon oxygen content, and meanwhile, the cage framework structure of POSS enables the POSS to have large volume and low dielectric property. The organic groups connected to the surface of the POSS silicone cage endow the POSS silicone cage with adjustability in performance and structure so as to improve the compatibility of the POSS silicone cage with an organic polymer resin matrix. In the prior art, POSS is introduced into other high molecular polymers as a polymerization monomer or an additive in a copolymerization/blending mode, so that the performance of the high molecular material can be improved.

At present, when POSS is blended and applied to improve the performances of other high polymer materials in the prior art, the phase separation phenomenon caused by poor miscibility exists, which can cause the performance of the materials to be reduced; when the properties of the polymer material are improved by introducing POSS through copolymerization, the properties of the polymer material are also influenced by the content of the introduced POSS. Therefore, there is an urgent need for a modified POSS compound that can undergo a thermal crosslinking reaction directly, and a high-performance polymer material having excellent atomic oxygen resistance, heat resistance, and low dielectric characteristics can be obtained by the thermal crosslinking reaction.

Disclosure of Invention

The embodiment of the invention provides polyhedral oligomeric silsesquioxane containing phenylethynyl and a synthesis method and application thereof, and provides polyhedral oligomeric silsesquioxane containing phenylethynyl to be directly crosslinked into a thermosetting high polymer with high temperature resistance, atomic oxygen resistance and low dielectric property by heating.

In a first aspect, the present invention provides a phenylethynyl-containing polyhedral oligomeric silsesquioxane, which is a compound having a structure shown in formula (i):

wherein the structural formula of the R group is

The structural formula of the A group is

In a second aspect, the present invention provides the method for synthesizing the phenylethynyl-containing polyhedral oligomeric silsesquioxane, which is characterized by comprising the following steps:

(1) adding 4-phenylethynyl phthalic anhydride with the A group, N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide and an organic solvent into a reactor for reaction to obtain a mixed solution containing the phenylethynyl-containing polyhedral oligomeric silsesquioxane;

(2) carrying out post-treatment on the mixed solution obtained in the step (1) to obtain the polyhedral oligomeric silsesquioxane containing phenylethynyl;

wherein the structural formula of the N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide is shown as the formula (II):

preferably, in the step (1), the reaction is carried out under the protection of nitrogen and in an oil bath for 6 to 12 hours under heating and refluxing.

Preferably, the molar mass ratio of the 4-phenylethynyl phthalic anhydride to the N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide is (2.2-5): 1.

Preferably, the ratio of the mass of the organic solvent to the sum of the mass of the 4-phenylethynylphthalic anhydride and the mass of the N- [ (heptaisobutylPOSS) propyl ] -3, 5-diaminobenzamide is (4-8): 1.

Preferably, the organic solvent is at least one of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, m-cresol and dimethyl sulfoxide.

Preferably, in step (2), the post-processing comprises the sub-steps of:

(i) carrying out reduced pressure distillation on the mixed solution obtained in the step (1) to obtain a concentrated solution;

(ii) and adding the concentrated solution into an alcohol solvent, heating and refluxing for 4-8h, cooling, separating, cleaning and drying in vacuum to obtain the polyhedral oligomeric silsesquioxane containing phenylethynyl.

Preferably, the mass ratio of the mixed solution to the concentrated solution is (3-7) to 1;

the mass ratio of the alcohol solvent to the concentrated solution is (2-6) to 1.

Preferably, the alcohol solvent is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol and ethylene glycol monomethyl ether.

Preferably, the drying temperature of the vacuum drying is 80-150 ℃, and the drying time is 8-24 h.

In a third aspect, the application of the polyhedral oligomeric silsesquioxane containing phenylethynyl groups in the first aspect or the polyhedral oligomeric silsesquioxane containing phenylethynyl groups obtained by the synthesis method in any one of the second aspects in preparing a thermosetting high polymer is characterized in that the polyhedral oligomeric silsesquioxane containing phenylethynyl groups is heated for a crosslinking reaction to obtain the thermosetting high polymer containing polyhedral oligomeric silsesquioxane.

Preferably, the reaction temperature of the crosslinking reaction is 330-400 ℃, and the reaction time is 1-6 h.

Compared with the prior art, the invention at least has the following beneficial effects:

(1) the novel polyhedral oligomeric silsesquioxane compound containing phenylethynyl is obtained by synthesizing amino polyhedral oligomeric silsesquioxane and phenylethynyl phthalic anhydride by a high-temperature one-step imidization method, and has low melt viscosity and high-temperature crosslinking characteristic; the compound has the advantages of simple synthesis method, high yield, simple and easy product purification process and the like;

(2) the synthesized cage type polysilsesquioxane contains a phenylethynyl group capable of being crosslinked by heat, can be used as a high-temperature-resistant thermosetting resin matrix, has low melting temperature, high heat resistance, low dielectric property and excellent atomic oxygen resisting property, solves the phase separation problem when the cage type polysilsesquioxane is used for improving the performance of other high polymer materials, can be used for preparing high-temperature-resistant wave-transmitting radome materials and atomic oxygen resisting coating materials, and has wide application in the aerospace field.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 shows the structure of a polyhedral oligomeric silsesquioxane compound containing phenylethynyl group synthesized in the examples of the present invention;

FIG. 2 is a nuclear magnetic resonance spectrum of a phenylethynyl-containing polyhedral oligomeric silsesquioxane compound synthesized in example 1 of the present invention;

FIG. 3 is an infrared spectrum of a phenylethynyl-containing polyhedral oligomeric silsesquioxane compound synthesized in example 1 of the present invention;

FIG. 4 is a DSC spectrum of a phenylethynyl-containing polyhedral oligomeric silsesquioxane compound synthesized in example 1 of the present invention;

FIG. 5 is a TGA curve of a POSS containing thermosetting high molecular polymer obtained in example 5 of the present invention;

FIG. 6 is a graph of the broadband dielectric properties of a POSS-containing thermosetting high molecular weight polymer obtained in example 5 of the present invention;

FIG. 7 is a mass loss curve of a POSS-containing thermosetting high molecular polymer obtained in example 5 of the present invention in an atomic oxygen environment.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts belong to the scope of the present invention.

The embodiment of the invention provides polyhedral oligomeric silsesquioxane containing phenylethynyl,

the polyhedral oligomeric silsesquioxane containing phenylethynyl is a compound with a structure shown as (I):

wherein the structural formula of the R group is

The structural formula of the A group is

In the present invention, the structure of the phenylethynyl-containing polyhedral oligomeric silsesquioxane compound is shown in fig. 1, wherein the introduction of the group a makes the compound have high-temperature crosslinking characteristics, and the structure of polyhedral oligomeric silsesquioxane makes the compound have lower melt viscosity.

It should be noted that the R group may also be an inert group such as alkyl, alkylene, aryl, etc., and may be used to adjust the compatibility between the POSS structure and the polymer. Preferably, the R group is isobutyl (i.e.)。

The invention provides a synthetic method of polyhedral oligomeric silsesquioxane containing phenylethynyl, which comprises the following steps:

(1) adding 4-phenylethynyl phthalic anhydride with the A group, N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide and an organic solvent into a reactor for reaction to obtain a mixed solution containing the phenylethynyl-containing polyhedral oligomeric silsesquioxane;

(2) carrying out post-treatment on the mixed solution obtained in the step (1) to obtain the polyhedral oligomeric silsesquioxane containing phenylethynyl;

wherein the structural formula of the N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide is shown as the formula (II):

in the invention, amino-containing polyhedral oligomeric silsesquioxane (namely N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide) and phenylethynyl phthalic anhydride are adopted to prepare the phenylethynyl-containing polyhedral oligomeric silsesquioxane compound by a high-temperature one-step imidization method, namely, the compound has high-temperature crosslinking characteristics due to the existence of phenylethynyl.

According to some preferred embodiments, in step (1), the reaction is heated under nitrogen protection in an oil bath for reflux reaction for 6-12h (for example, 6h, 7h, 8h, 9h, 10h, 11h or 12h may be used).

According to some preferred embodiments, the molar mass ratio of the 4-phenylethynyl phthalic anhydride to the N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide is (2.2-5):1 (e.g., may be 2.2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5: 1).

According to some preferred embodiments, the ratio of the mass of the organic solvent to the sum of the mass of the 4-phenylethynylphthalic anhydride and the mass of the N- [ (heptaisobutylposs) propyl ] -3, 5-diaminobenzamide is (4-8: 1 (e.g., may be 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, or 8: 1).

According to some preferred embodiments, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, m-cresol, dimethylsulfoxide.

At least one of them is a mixture of any one or any several of them mixed in any ratio.

It should be noted that the heating temperature in the step (1) is a temperature value not lower than the boiling point of the organic solvent. For example, when the organic solvent in step (1) is N, N-dimethylformamide, the heating temperature in step (1) is not lower than 153 ℃ of its boiling point (for example, may be 158 ℃, 160 ℃, 163 ℃, or the like); when the organic solvent in the step (1) comprises N, N-dimethylacetamide, the heating temperature of the step (1) is not lower than 164 ℃ of the boiling point thereof; when the organic solvent in the step (1) comprises N-methyl pyrrolidone and/or m-cresol, the heating temperature of the step (1) is not lower than the boiling point of 203 ℃; when the organic solvent in step (1) comprises dimethyl sulfoxide, the heating temperature in step (1) is not lower than 189 ℃ which is the boiling point thereof.

According to some preferred embodiments, in step (2), the post-processing comprises the following sub-steps:

(i) carrying out reduced pressure distillation on the mixed solution obtained in the step (1) to obtain a concentrated solution;

(ii) and adding the concentrated solution into an alcohol solvent, heating and refluxing for 4-8h, cooling, separating, cleaning and drying in vacuum to obtain the polyhedral oligomeric silsesquioxane containing phenylethynyl.

In the present invention, most of the organic solvent in step (1) is removed by distillation under reduced pressure to obtain a concentrated solution containing the objective compound, i.e., phenylethynyl-containing polyhedral oligomeric silsesquioxane. Adding an alcohol reagent into the concentrated solution for heating reflux reaction, so that unreacted 4-phenylethynyl phthalic anhydride reacts with the alcohol reagent to generate monoester monoacid easily soluble in the alcohol reagent, and the unreacted 4-phenylethynyl phthalic anhydride in the concentrated solution is completely removed.

Experiments prove that the condensed liquid is added into an alcohol solvent and heated and refluxed for 4-8h (for example, 4h, 5h, 6h, 7h or 8h), after the condensed liquid is cooled to room temperature (for example, 25 ℃), the solid in the condensed liquid is separated by filtration, and then the solid is washed by deionized water and then dried in vacuum, so that the polyhedral oligomeric silsesquioxane containing phenylethynyl is obtained.

According to some preferred embodiments, the mass ratio of the mixed solution to the concentrated solution is (3-7): 1;

the mass ratio of the alcohol solvent to the concentrated solution is (2-6) to 1.

Experiments prove that the mass ratio of the mixed solution to the concentrated solution is (3-7) to 1 (for example, 3:1, 4:1, 5:1, 6:1 or 7: 1); the mass ratio of the alcohol solvent to the concentrated solution is (2-6):1 (for example, 2:1, 3:1, 4:1, 5:1 or 6: 1).

According to some preferred embodiments, in the step (2), the alcoholic solvent is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, and ethylene glycol monomethyl ether.

It should be noted that the heating temperature in the step (2) is a temperature not lower than the boiling point of the alcohol solvent.

According to some preferred embodiments, in the step (2), the drying temperature of the vacuum drying is 80-150 ℃ and the drying time is 8-24 h.

Experiments prove that the drying temperature of the vacuum drying is 80-150 ℃ (for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃), and the drying time is 8-24h (for example, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h).

The invention also provides application of the polyhedral oligomeric silsesquioxane containing phenylethynyl, and the polyhedral oligomeric silsesquioxane containing phenylethynyl is prepared by utilizing the synthetic polyhedral oligomeric silsesquioxane containing phenylethynyl to carry out thermal crosslinking reaction.

According to some preferred embodiments, the reaction temperature of the crosslinking reaction is 330-400 ℃ and the reaction time is 1-6 h.

Experiments prove that the reaction temperature of the crosslinking reaction can be 330-400 ℃ (for example, 330 ℃, 350 ℃, 360 ℃, 380 ℃ or 400 ℃), and the reaction time can be 1-6h (for example, 1h, 2h, 3h, 4h, 5h or 6 h).

The thermosetting high molecular polymer containing the cage polysilsesquioxane obtained by the invention has excellent temperature resistance, atomic oxygen resistance and low dielectric property.

In order to more clearly illustrate the technical scheme and advantages of the present invention, the following examples are provided to describe the synthesis method and application of polyhedral oligomeric silsesquioxane containing phenylethynyl group in detail.

In the following examples:

amino group-containing cage polysilsesquioxane (i.e., N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide) was synthesized by the present inventors by the method shown in FIG. 2 of the Atomic-Oxygen Effects on POSS polymers in Low Earth Orbit (Minton T K, Wright M E, Tomczak S J, et al. Atomic-Oxygen Effects on POSS polymers in Low Earth Orbit [ J ]. Applied Materials & Interfaces,2012,4(2): 492) literature published by Minton T K et al, specifically, a dichloromethane solution containing 3-aminopropyl (heptaisobutyl) POSS and triethylamine and 3, 5-dinitrobenzoyl chloride are placed at 0 ℃ for reaction to obtain a mixed solution containing N- [ (heptaisobutyl POSS) propyl ] -3, 5-dinitrobenzamide; then, taking platinum dioxide as a catalyst, adding tetrahydrofuran and ethanol, reacting in a hydrogen atmosphere, and converting nitro into amino to finally obtain N- [ (heptaisobutyl POSS propyl ] -3, 5-diaminobenzamide;

4-Phenylethynylphthalic anhydride was purchased from Fosmann technologies (Beijing) Inc.

Example 1: synthesis of polyhedral oligomeric silsesquioxane containing phenylethynyl

(1) 24.842g (0.1mol) of 4-phenylethynyl phthalic anhydride, 25.218g (0.025mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide and 300.36g of nitrogen-nitrogen Dimethylformamide (DMF) are added into a three-neck round-bottom flask, the three-neck flask is connected with a nitrogen protection device and a reflux condenser, then the three-neck flask is put into an oil bath at 160 ℃, and the heating reflux reaction is carried out for 8 hours, so as to obtain a mixed solution containing the target compound (namely, the phenylethynyl-containing polyhedral oligomeric silsesquioxane);

(2) carrying out reduced pressure distillation on the mixed solution obtained in the step (1) by using a reduced pressure distillation device until the mass of the residual concentrated solution is 87g, and stopping the reduced pressure distillation to obtain a concentrated solution;

the concentrated solution was put into a single-neck flask containing 350g of absolute ethanol, and heated under reflux at 85 ℃ for 6 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered and separated at normal pressure to obtain a filter cake, which was washed twice with deionized water, and then the obtained solid was placed in a vacuum oven and dried at 120 ℃ for 12 hours to obtain 34.57g of the target compound (i.e., polyhedral oligomeric silsesquioxane containing phenylethynyl group), wherein the yield was 94.1%.

Structural characterization is carried out on the polyhedral oligomeric silsesquioxane containing phenylethynyl group obtained in example 1, and the nuclear magnetic hydrogen spectrum, the infrared spectrum and the DSC spectrogram are respectively shown in fig. 2, fig. 3 and fig. 4. The nuclear magnetic hydrogen spectrum of FIG. 2 is consistent with the theoretical mass/charge ratio; FIG. 3 shows an infrared spectrum corresponding to the theoretical inclusion of groups of 1350cm^-1The imine ring peak shows that the amino-containing polyhedral oligomeric silsesquioxane is imidized with phenylethynyl phthalic anhydride. As can be seen from the DSC chart of fig. 4, as the temperature gradually increases, 1 endothermic peak and 1 exothermic peak occur; wherein the endothermic peak is a melting peak, the melting temperature is about 230 ℃, the solidification heat release begins to appear at about 330 ℃ along with the increase of the temperature, and the peak temperature of the exothermic peak is 400 ℃, so that the crosslinking and solidification temperature of the phenylethynyl-containing polyhedral oligomeric silsesquioxane is determined to be 330-400 ℃.

Example 2: synthesis of polyhedral oligomeric silsesquioxane containing phenylethynyl

(1) 13.663g (0.055mol) of 4-phenylethynyl phthalic anhydride, 25.218g (0.025mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide and 155.53g of nitrogen-nitrogen Dimethylformamide (DMF) are added into a three-neck round-bottom flask, the three-neck flask is connected with a nitrogen protection device and a reflux condensation device, then the three-neck flask is added into an oil bath at 160 ℃, and the mixture is heated and refluxed for 6 hours to obtain a mixed solution containing a target compound (namely, the polyhedral oligomeric silsesquioxane containing phenylethynyl);

(2) carrying out reduced pressure distillation on the mixed solution obtained in the step (1) by using a reduced pressure distillation device until the mass of the residual concentrated solution is 64.4g, and stopping the reduced pressure distillation to obtain a concentrated solution;

the concentrated solution was put into a single-neck flask containing 128.8g of absolute ethanol, and heated under reflux at 85 ℃ for 4 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered and separated at normal pressure to obtain a filter cake, which was washed twice with deionized water, and then the obtained solid was placed in a vacuum oven and dried at 80 ℃ for 24 hours to obtain 33.14g of the target compound (i.e., polyhedral oligomeric silsesquioxane containing phenylethynyl group), wherein the yield was 90.2%.

Example 3: synthesis of polyhedral oligomeric silsesquioxane containing phenylethynyl

(1) 37.263g (0.15mol) of 4-phenylethynyl phthalic anhydride, 50.436g (0.05mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide and 438.50g of nitrogen methyl pyrrolidone are added into a three-neck round-bottom flask, the three-neck flask is connected with a nitrogen protection device and a reflux condensation device, then the three-neck flask is added into an oil bath at 213 ℃, and the mixture is heated and refluxed for 10 hours to obtain a mixed solution containing a target compound (namely, the polyhedral oligomeric silsesquioxane containing phenylethynyl);

(2) carrying out reduced pressure distillation on the mixed solution obtained in the step (1) by using a reduced pressure distillation device until the mass of the residual concentrated solution is 105.2g, and stopping the reduced pressure distillation to obtain a concentrated solution;

the concentrated solution was put into a single-neck flask containing 315.72g of n-propanol and heated under reflux at 105 ℃ for 8 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered and separated at normal pressure to obtain a filter cake, which was washed twice with deionized water, and then the obtained solid was placed in a vacuum oven and dried at 100 ℃ for 16 hours to obtain 68.70g of the target compound (i.e., polyhedral oligomeric silsesquioxane containing phenylethynyl group), wherein the yield was 93.5%.

Example 4: synthesis of polyhedral oligomeric silsesquioxane containing phenylethynyl

(1) 55.894g (0.25mol) of 4-phenylethynyl phthalic anhydride, 50.436g (0.05mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide and 850.64g of dimethyl sulfoxide are added into a three-neck round-bottom flask, the three-neck flask is connected with a nitrogen protection device and a reflux condensing device, then the three-neck flask is added into an oil bath at 213 ℃, and the mixture is heated and refluxed for 10 hours to obtain a mixed solution containing a target compound (namely, the phenylethynyl-containing polyhedral oligomeric silsesquioxane);

(2) carrying out reduced pressure distillation on the mixed solution obtained in the step (1) by using a reduced pressure distillation device, and stopping the reduced pressure distillation until the mass of the residual concentrated solution is 136.7g to obtain a concentrated solution;

the concentrated solution was put into a one-neck flask containing 683.5g of ethylene glycol monomethyl ether, and heated under reflux at 135 ℃ for 7 hours. After the reaction solution was cooled to room temperature, the reaction solution was filtered and separated at normal pressure to obtain a filter cake, which was washed twice with deionized water, and then the obtained solid was placed in a vacuum oven and dried at 150 ℃ for 8 hours to obtain 69.73g of the target compound (i.e., polyhedral oligomeric silsesquioxane containing phenylethynyl group), wherein the yield was 94.9%.

Example 5: application of polyhedral oligomeric silsesquioxane containing phenylethynyl

The polyhedral oligomeric silsesquioxane compound containing phenylethynyl groups synthesized in example 1 was placed in a stainless steel mold, and then the mold was placed in a high-temperature air oven, and after curing at 350 ℃/2h and 370 ℃/1h, the mold was furnace-cooled to room temperature and then taken out of the mold, thereby obtaining a thermosetting high-molecular polymer containing POSS (i.e., a thermosetting high-molecular polymer of polyhedral oligomeric silsesquioxane containing phenylethynyl groups).

The TGA curve (thermogravimetric curve) of the POSS-containing thermosetting high molecular polymer obtained in example 5 is shown in fig. 5, wherein the thermal decomposition temperature of 5% weight loss of the thermosetting high molecular polymer is 527.4 ℃, and the thermal decomposition temperature of 5% weight loss of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide is 510.4 ℃, so that the thermosetting high molecular polymer has more excellent high temperature resistance; the broadband dielectric property curve of the POSS-containing thermosetting high-molecular polymer is shown in FIG. 6, wherein the thermosetting high-molecular polymer has excellent electrical property, dielectric constant of about 2.85 and dielectric loss of about 0.008 under the frequency of 1-12GHz, and low dielectric property; the mass loss curve of the POSS-containing thermosetting high molecular polymer (i.e., the POSS-containing thermosetting high molecular polymer in fig. 7) in an atomic oxygen environment is shown in fig. 7, and the mass loss of the POSS-containing thermosetting high molecular polymer sample is smaller than that of the standard Kapton (a film of a homopolyphenylene polyimide, for example, a dupont Kapton HN film in this example), and the mass loss of the POSS-containing thermosetting high molecular polymer sample is 2.77% after being treated with atomic oxygen for 60 hours, while the mass loss of the standard Kapton sample is 19.50%, so that the POSS-containing thermosetting high molecular polymer has excellent atomic oxygen resistance.

Examples 6 to 8

Examples 6 to 8 thermosetting high molecular polymers were prepared in the same manner as in example 5 using the phenylethynyl-containing polyhedral oligomeric silsesquioxane prepared in examples 2 to 4, respectively. Specifically, the polyhedral oligomeric silsesquioxane containing phenylethynyl is placed in a stainless steel mold, then the mold is placed in a high-temperature blast oven, and after the curing procedures of 350 ℃/2h and 370 ℃/1h, the mold is cooled to room temperature along with the furnace and then taken out of the mold, so that the thermosetting high polymer containing POSS is obtained.

The thermosetting high molecular polymers prepared in examples 6 to 8 were tested in the same manner as in example 5, and the test results are shown in table 1:

TABLE 1

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.