A process for the preparation of an aminophenyl oligosilsesquioxane

Abstract

The application provides an aminophenyl oligosilsesquioxane, a preparation method and application thereof, and a polymer material, and belongs to the technical field of organic-inorganic hybrid materials.The application provides a preparation method of an aminophenyl oligosilsesquioxane, which comprises the following steps: mixing nitrophenyl oligosilsesquioxane, a reducing agent and a solvent, and performing a reduction reaction under the condition that no catalyst is used or at least one of 4,4'-dipyridyl, diphenylamine, 2,2'-dipyridyl and pyridine is used as a catalyst to obtain the aminophenyl oligosilsesquioxane; the reducing agent is a diboron compound.The preparation method provided by the application has high yield, strong universality, low cost, is environment-friendly, and is suitable for industrial production; the aminophenyl oligosilsesquioxane prepared by the method has good structural stability and can be used for preparing high-performance polymer materials.

Description

Technical Field

[0001] This invention belongs to the field of organic-inorganic hybrid materials technology, specifically relating to an aminophenyl oligomeric silsesquioxane, its preparation method and application, and polymer materials. Background Technology

[0002] Polyhedral oligomeric silsesquioxanes (POSS) are nanoscale organic-inorganic hybrid materials that combine the advantages of both organic and inorganic materials. Among them, phenyl POSS is a type with the chemical formula (PhSiO₂). 1.5 ) n The oligomeric silsesquioxane contains a cage-like rigid inorganic Si-O-Si core. Preparing polymer materials by co-integrating phenyl POSS with a polymer matrix improves the thermal stability, flame retardancy, mechanical properties, and dielectric properties of the resulting polymers. However, due to the poor solubility of phenyl POSS, it is mostly dispersed in the polymer matrix as microparticles, leading to uneven dispersion and affecting the performance of the polymer materials. Amino compounds possess good chemical reactivity and solubility, and can react with various groups. Therefore, converting phenyl to aminophenyl via side-group conversion can enhance the solubility and reactivity of phenyl POSS in the polymer matrix, enabling molecular-level dispersion in the polymer matrix through physical mixing or chemical reaction. Therefore, the synthesis and preparation of aminophenyl POSS is of great significance.

[0003] Currently, in existing technologies, aminophenyl POSS is typically prepared using hydrazine hydrate as a reducing agent in the presence of a catalyst. For example, patent CN 100412077C discloses a method for preparing aminophenyl silsesquioxanes, which uses Fe / C as a catalyst; patent CN 100430406C discloses a method for preparing octaaminophenyl cage-like silsesquioxanes, which uses an aluminum compound or a mixture of aluminum and iron compounds as a catalyst; and patent CN 102391303A discloses a method for preparing cage-like oligomeric octaaminophenyl oligomeric silsesquioxanes, which uses ferric chloride and palladium on carbon as catalysts.

[0004] All three existing solutions mentioned above use hydrazine hydrate, which has a strong alkalinity, as a reducing agent. However, silicon-oxygen bonds are prone to breakage under alkaline conditions, which may destroy the cage-like structure of the resulting cage-like octaminophenyl oligomeric silsesquioxane, thus hindering its application in polymer materials. Summary of the Invention

[0005] The purpose of this invention is to provide an aminophenyl oligomeric silsesquioxane, its preparation method, applications, and polymer materials. The aminophenyl oligomeric silsesquioxane obtained according to the preparation method provided by this invention has good structural stability and can be used to prepare high-performance polymer materials.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a method for preparing aminophenyl oligomeric silsesquioxane, comprising the following steps:

[0008] Nitrophenyl oligosilsesquioxane, a reducing agent, and a solvent are mixed and subjected to a reduction reaction under conditions without a catalyst or with at least one of 4,4'-bipyridine, diphenylamine, 2,2'-bipyridine, and pyridine as a catalyst to obtain aminophenyl oligosilsesquioxane; the reducing agent is a diborone compound.

[0009] Preferably, the nitrophenyl oligomeric silsesquioxane includes at least one of T8 cage-like nitrophenyl oligomeric silsesquioxane, T12 cage-like nitrophenyl oligomeric silsesquioxane, and Tn cyclic ladder-like nitrophenyl oligomeric silsesquioxane.

[0010] Preferably, the diboron compound includes at least one of tetrahydroxydiboron, neopentyl glycol diborate, pinacol diborate, and bis(catechol)boronic acid; the molar ratio of the nitro functional group of the nitrophenyl oligosilsesquioxane to the reducing agent is 1:1 to 6.

[0011] Preferably, the solvent includes at least one of ethanol, ethyl acetate, dichloromethane, tetrahydrofuran, and N,N-dimethylformamide; the ratio of the nitrophenyl oligomeric silsesquioxane to the solvent is 1 g: 1-40 mL.

[0012] Preferably, the amount of catalyst does not exceed 5% of the amount of nitro functional group of nitrophenyl oligosilsesquioxane.

[0013] Preferably, the reduction reaction is carried out in an inert atmosphere; the inert atmosphere includes at least one of nitrogen and argon.

[0014] Preferably, the reduction reaction is carried out at a temperature of 20–80°C for 2–24 hours.

[0015] This invention provides an aminophenyl oligomeric silsesquioxane prepared by the preparation method described in the above technical solution.

[0016] This invention provides the application of the aminophenyl oligomeric silsesquioxane described in the above technical solution in polymer materials.

[0017] The present invention provides a polymer material comprising the aminophenyl oligomeric silsesquioxane described in the above technical solution and a polymer matrix; the polymer matrix comprises at least one of epoxy resin and polyimide.

[0018] This invention provides a method for preparing aminophenyl oligomeric silsesquioxanes, comprising the following steps: mixing nitrophenyl oligomeric silsesquioxanes, a reducing agent, and a solvent, and carrying out a reduction reaction under conditions without a catalyst or with at least one of 4,4'-bipyridine, diphenylamine, 2,2'-bipyridine, and pyridine as a catalyst to obtain aminophenyl oligomeric silsesquioxanes; wherein the reducing agent is a diborone compound. This invention uses a diborone compound as a reducing agent, which on the one hand enables reduction under conditions without expensive catalysts, simplifying the preparation process and reducing preparation costs; on the other hand, the diborone compound, in combination with catalysts such as 4,4'-bipyridine, constructs a highly efficient catalytic system, greatly improving the reaction rate. The preparation method of this invention has mild and stable reaction conditions, applicable to the reduction of different nitrophenyl oligomeric silsesquioxanes; the process has good repeatability and broad applicability, and also features low cost, environmental friendliness, and simple operation, making it suitable for industrial production. Furthermore, the preparation method provided by this invention has high yield and the obtained aminophenyl oligomeric silsesquioxanes have good structural stability, making it suitable for large-scale production.

[0019] Furthermore, the aminophenyl oligomeric silsesquioxane obtained by the preparation method described in this invention can be further reacted to obtain POSS containing different functional groups, or it can be introduced into polymer matrices such as epoxy resin and polyimide through various means such as grafting, crosslinking and copolymerization, thereby improving the flame retardancy, dielectric properties, mechanical properties and other properties of the obtained polymer material. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 The FTIR spectrum of T8 cage-like aminophenyl oligomeric silsesquioxane prepared in Example 1;

[0022] Figure 2 The T8 cage-like aminophenyl oligomeric silsesquioxane prepared in Example 1 1 H NMR spectrum;

[0023] Figure 3 The mass spectrum of T8 cage-like aminophenyl oligomeric silsesquioxane prepared in Example 1 is shown. Detailed Implementation

[0024] This invention provides a method for preparing aminophenyl oligomeric silsesquioxane, comprising the following steps:

[0025] Nitrophenyl oligosilsesquioxane, a reducing agent, and a solvent are mixed and subjected to a reduction reaction under conditions without a catalyst or with at least one of 4,4'-bipyridine, diphenylamine, 2,2'-bipyridine, and pyridine as a catalyst to obtain aminophenyl oligosilsesquioxane; the reducing agent is a diborone compound.

[0026] In this invention, unless otherwise specified, all raw materials used are commercially available products well known to those skilled in the art or prepared using methods well known to those skilled in the art.

[0027] This invention involves mixing nitrophenyl oligosilsesquioxane, a reducing agent, and a solvent, and carrying out a reduction reaction under conditions without a catalyst or with 4,4'-bipyridine as a catalyst to obtain aminophenyl oligosilsesquioxane.

[0028] In this invention, the nitrophenyl oligomeric silsesquioxane preferably includes at least one of T8 cage-like nitrophenyl oligomeric silsesquioxane, T12 cage-like nitrophenyl oligomeric silsesquioxane, and Tn cyclic ladder-like nitrophenyl oligomeric silsesquioxane, more preferably T8 cage-like nitrophenyl oligomeric silsesquioxane, T12 cage-like nitrophenyl oligomeric silsesquioxane, or Tn cyclic ladder-like nitrophenyl oligomeric silsesquioxane. The T8 cage-like nitrophenyl oligomeric silsesquioxane (nitro functionality 1-8) is preferably T8 cage-like low-nitrofunctional phenyl cage-like silsesquioxane (nitro functionality 1-7); the T12 cage-like nitrophenyl oligomeric silsesquioxane (nitro functionality 1-12) preferably includes T12 cage-like low-nitrofunctional phenyl oligomeric silsesquioxane (nitro functionality 1-11).

[0029] In this invention, the reducing agent is a diboron compound; the diboron compound preferably includes at least one selected from tetrahydroxydiboron, neopentyl glycol diborate, pinacol diborate, and bis(catechol)boronic acid, more preferably tetrahydroxydiboron or neopentyl glycol diborate. The molar ratio of the nitro functional group of the nitrophenyl oligomeric silsesquioxane to the reducing agent is preferably 1:1 to 6, more preferably 1:2 to 5.

[0030] In this invention, the solvent preferably includes at least one selected from ethanol, ethyl acetate, dichloromethane, tetrahydrofuran, and N,N-dimethylformamide, more preferably dichloromethane or N,N-dimethylformamide. The feed-to-liquid ratio of the nitrophenyl oligomeric silsesquioxane to the solvent is preferably 1g:1-40mL, more preferably 1g:10-30mL.

[0031] This invention involves a reduction reaction carried out without a catalyst or with at least one of 4,4'-bipyridine, diphenylamine, 2,2'-bipyridine, and pyridine as a catalyst. In this invention, when a catalyst is used for the reduction reaction, the catalyst is preferably 4,4'-bipyridine. In this invention, the amount of the catalyst is preferably no more than 5% of the amount of the nitro functional group of the nitrophenyl oligosilsesquioxane, more preferably no more than 4% of the amount of the nitro functional group of the nitrophenyl oligosilsesquioxane. In one embodiment of this invention, the amount of the catalyst is 0. In another embodiment of this invention, the amount of the catalyst is 0.1% to 3% of the amount of the nitro functional group of the nitrophenyl oligosilsesquioxane.

[0032] The reduction reaction of the present invention is preferably carried out in an inert atmosphere; the inert atmosphere preferably includes at least one of nitrogen and argon, more preferably nitrogen. The temperature of the reduction reaction of the present invention is preferably 20-80°C, more preferably 30-50°C, and the time is preferably 2-24 h, more preferably 10-24 h. The reduction reaction of the present invention is preferably carried out under stirring.

[0033] After the reduction reaction, the present invention preferably mixes the obtained material with ethyl acetate, washes it with saturated brine, separates the liquids, mixes the obtained organic phase with a precipitant, and precipitates the precipitate; collects the precipitate by solid-liquid separation, and dries the precipitate to obtain aminophenyl oligomeric silsesquioxane. In the present invention, the washing is preferably performed 2 to 3 times, more preferably 3 times. In the present invention, the precipitant is preferably at least one selected from n-hexane, petroleum ether, benzene, water, and cyclohexane, more preferably n-hexane or petroleum ether; the volume ratio of the organic phase to the precipitant is preferably 1:1 to 20, more preferably 1:5 to 15. The solid-liquid separation in the present invention is preferably vacuum filtration; the drying is preferably vacuum drying.

[0034] This invention also provides an aminophenyl oligomeric silsesquioxane prepared by the preparation method described in the above technical solution. The aminophenyl oligomeric silsesquioxane of this invention preferably includes at least one of T8 cage-type aminophenyl oligomeric silsesquioxane, T12 cage-type aminophenyl oligomeric silsesquioxane, and Tn cyclic ladder-type aminophenyl oligomeric silsesquioxane, more preferably T8 cage-type aminophenyl oligomeric silsesquioxane, T12 cage-type aminophenyl oligomeric silsesquioxane, or Tn cyclic ladder-type aminophenyl oligomeric silsesquioxane.

[0035] In this invention, when the nitrophenyl oligosilsesquioxane is a T8 cage-like nitrophenyl oligosilsesquioxane, the resulting aminophenyl oligosilsesquioxane is preferably a T8 cage-like aminophenyl oligosilsesquioxane. The T8 cage-like aminophenyl oligosilsesquioxane of this invention preferably has the structure shown in Formula I:

[0036]

[0037] In Formula I, each R is independently either phenyl or aminophenyl, and at least one R is aminophenyl.

[0038] In this invention, when the nitrophenyl oligosilsesquioxane is a T8 cage-shaped low-nitrofunctional phenyl cage-shaped silsesquioxane, the resulting aminophenyl oligosilsesquioxane is preferably a T8 cage-shaped aminophenyl oligosilsesquioxane.

[0039] In this invention, when the nitrophenyl oligosiloxyalkylene is a T12 cage-like nitrophenyl oligosiloxyalkylene, the resulting aminophenyl oligosiloxyalkylene is preferably a T12 cage-like aminophenyl oligosiloxyalkylene. The T12 cage-like aminophenyl oligosiloxyalkylene of this invention preferably has the structure shown in Formula II:

[0040]

[0041] In Formula II, each R is independently either phenyl or aminophenyl, and at least one R is amino.

[0042] In this invention, when the nitrophenyl oligomeric silsesquioxane is a T12 cage-like low-nitrofunctional phenyl cage-like silsesquioxane, the resulting aminophenyl oligomeric silsesquioxane is preferably a T12 cage-like aminophenyl oligomeric silsesquioxane.

[0043] In this invention, when the nitrophenyl oligosilsesquioxane is a Tn-ring ladder-shaped nitrophenyl oligosilsesquioxane, the resulting aminophenyl oligosilsesquioxane is preferably a Tn-ring ladder-shaped aminophenyl oligosilsesquioxane. The Tn-ring ladder-shaped aminophenyl oligosilsesquioxane of this invention preferably has the structure shown in Formula III:

[0044]

[0045] In Formula III, n ≥ 2 (preferably n = 30) and n is an integer; each R is independently phenyl or aminophenyl, and at least one R is amino.

[0046] The present invention also provides the application of the aminophenyl oligomeric silsesquioxane described in the above technical solution in polymer materials.

[0047] The present invention also provides a polymer material comprising the aminophenyl oligomeric silsesquioxane described in the above technical solution and a polymer matrix; the polymer matrix comprises at least one of epoxy resin and polyimide, preferably epoxy resin or polyimide.

[0048] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0049] The three-necked flask used in the embodiment is equipped with a reflux condenser, a constant pressure dropping funnel, a temperature control device, a nitrogen protection device, and a magnetic stirring device.

[0050] Example 1

[0051] 1) Add 5g of T8 cage-shaped nitrophenyl oligomeric silsesquioxane, 0.023g of 4,4'-bipyridine and 100mL of N,N-dimethylformamide to a three-necked flask to obtain a mixture; under stirring and nitrogen protection, add 50mL of N,N-dimethylformamide solution containing 8g of tetrahydroxydiboron dropwise to the mixture. After the addition is complete, react at 30℃ for 10h to obtain the reaction solution.

[0052] 2) Add 100 mL of ethyl acetate to the reaction mixture, wash three times with saturated brine, pour the organic phase into 200 mL of n-hexane, and precipitate (light brown); filter the precipitate, and vacuum dry the resulting solid material to obtain T8 cage-like aminophenyl oligomeric silsesquioxane with a yield of 88.7%.

[0053] The T8 cage-like aminophenyl oligomeric silsesquioxane obtained in Example 1 was subjected to infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and mass spectrometry, respectively. The results are as follows: Figure 1 , 2 As shown in Figure 3.

[0054] Depend on Figure 1 It can be seen that at 3500cm -1 The characteristic absorption peak of the -OH group, which does not show the open siloxane cage structure in the vicinity, is at 1080 cm⁻¹. -1 The absorption peak at this point is attributed to the vibration of the Si-O-Si bond, preliminarily indicating that most or all of the siloxane cage structure remains intact. An infrared spectrum at 3480.2 cm⁻¹ appears. -1 3360.6cm -1 and 3220.3cm -1 The characteristic amino peak was observed, but the characteristic absorption peak of the nitro system at 1530 cm⁻¹ was not present. -1 1350cm -1 It can be preliminarily determined that the cage-like octanitrophenyl oligosilsesquioxane is quantitatively converted into cage-like octanitrophenyl oligosilsesquioxane.

[0055] Figure 2 In the T8 cage-like aminophenyl oligomeric silsesquioxane, H atoms are located on the amino and benzene rings, respectively. The peaks of hydrogen atoms on the phenyl ring are 6.0–8.0 ppm, and the peaks of hydrogen atoms on the amino ring are 4.0–6.0 ppm. The ratio of the integrated area of ​​the amino hydrogen atom peak to the integrated area of ​​the phenyl hydrogen atom peak is close to the theoretical value of 0.5:1, indicating that the nitro groups connected to the benzene ring are successfully reduced to amino groups.

[0056] Finally, the commonly used characterization method for measuring the molecular weight of octaaminophenyl oligosilsesquioxanes is GPC. This invention introduces MALDI TOF MS for molecular weight characterization. Figure 3 It is evident that the T8 cage-like aminophenyl oligomeric silsesquioxane prepared by this invention has a stable structure. The results demonstrate that this invention synthesizes a structurally complete octaaminophenyl oligomeric silsesquioxane, further illustrating the mildness and effectiveness of the preparation method described in this invention.

[0057] Example 2

[0058] 1) Add 10g of T8 cage-shaped nitrophenyl oligomeric silsesquioxane and 100mL of N,N-dimethylformamide to a three-necked flask to obtain a mixture; under stirring and nitrogen protection, add 100mL of N,N-dimethylformamide solution containing 15g of tetrahydroxydiboron dropwise to the mixture. After the addition is complete, react at 60℃ for 24h to obtain the reaction solution.

[0059] 2) Add 200 mL of ethyl acetate to the reaction mixture, wash three times with saturated brine, pour the organic phase into 400 mL of n-hexane, and precipitate (light brown); filter the precipitate, and vacuum dry the resulting solid material to obtain T8 cage-like aminophenyl oligomeric silsesquioxane with a yield of 85.7%.

[0060] Example 3

[0061] 1) Add 5g of T8 cage-shaped low-nitrate functional phenyl cage-shaped silsesquioxane, 0.023g of 4,4'-bipyridine and 100mL of N,N-dimethylformamide to a three-necked flask to obtain a mixture; under stirring and nitrogen protection, add 50mL of N,N-dimethylformamide solution containing 8g of tetrahydroxydiboron dropwise to the mixture. After the addition is complete, react at 30℃ for 10h to obtain the reaction solution.

[0062] 2) Add 200 mL of ethyl acetate to the reaction mixture, wash three times with saturated brine, pour the organic phase into 200 mL of n-hexane, and precipitate (light brown); filter the precipitate, and vacuum dry the resulting solid material to obtain T8 cage-like low-amino-functionality phenyl oligomeric silsesquioxane with a yield of 82.6%.

[0063] Example 4

[0064] 1) Add 5g of T12 cage-like nitrophenyl oligomeric silsesquioxane, 0.025g of 4,4'-bipyridine and 100mL of N,N-dimethylformamide to a three-necked flask to obtain a mixture; under stirring and nitrogen protection, add 50mL of N,N-dimethylformamide solution containing 12g of tetrahydroxydiboron dropwise to the mixture. After the addition is complete, react at 30℃ for 24h to obtain the reaction solution.

[0065] 2) Add 200 mL of ethyl acetate to the reaction mixture, wash three times with saturated brine, pour the organic phase into 400 mL of n-hexane, and precipitate (light brown); filter the precipitate, and vacuum dry the resulting solid material to obtain T12 cage-like aminophenyl oligomeric silsesquioxane with a yield of 80.5%.

[0066] Example 5

[0067] 1) Add 5g of T12 cage-shaped low-nitrofunctional phenyl oligomeric silsesquioxane, 0.025g of 4,4'-bipyridine and 100mL of N,N-dimethylformamide to a three-necked flask to obtain a mixture; under stirring and nitrogen protection, add 75mL of N,N-dimethylformamide solution containing 12g of tetrahydroxydiboron dropwise to the mixture. After the addition is complete, react at 25℃ for 24h to obtain the reaction solution.

[0068] 2) Add 200 mL of ethyl acetate to the reaction mixture, wash three times with saturated brine, pour the organic phase into 400 mL of n-hexane, and precipitate (light brown); filter the precipitate, and vacuum dry the resulting solid material to obtain T12 cage-like low-amino-functionality phenyl oligomeric silsesquioxane with a yield of 78.5%.

[0069] Comparative Example 1

[0070] The experiment was conducted with reference to the patent with publication number CN 102391303A, and the specific operation is as follows:

[0071] 1) Weigh 15g of T8 cage-shaped nitrophenyl oligomeric silsesquioxane and add it to a three-necked flask. Dissolve it in 120mL of tetrahydrofuran, then add 1.83g of 5% Pd / C catalyst and 0.6g of ferric chloride hexahydrate. Heat the mixture to 60℃ and slowly add 48mL of 80% hydrazine hydrate under nitrogen protection. Reflux the mixture for 12h. After the reaction is complete, the reaction solution is obtained.

[0072] 2) Add 120 mL of ethyl acetate to the reaction mixture, let stand until the black catalyst Pd / C layer separates from the organic layer, filter the organic layer, wash it once with 360 mL of saturated brine, dry it with anhydrous sodium sulfate, pour it into 1000 mL of n-hexane, a white precipitate precipitates, filter it, dry it in a vacuum oven, and obtain T8 cage-like low-amino-functionality phenyl oligomeric silsesquioxane with a yield of 75.2%.

[0073] The product yield of Comparative Example 1 was significantly lower than that of Examples 1-3. Furthermore, Comparative Example 1 used a precious metal catalyst, which increased the cost and also made the post-processing more complex.

[0074] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1.A method for preparing an aminophenyl oligosilsesquioxane, comprising the following steps: mixing a nitrophenyl oligosilsesquioxane, a reducing agent and a solvent to perform a reduction reaction without a catalyst to obtain an aminophenyl oligosilsesquioxane; the reducing agent is a diboron compound; the solvent is N, N-dimethylformamide; the reduction reaction is performed at a temperature of 50-80℃ for 24 hours; and the reduction reaction is performed in an inert atmosphere; wherein the nitrophenyl oligosilsesquioxane comprises at least one of a T8 cage-shaped nitrophenyl oligosilsesquioxane, a T12 cage-shaped nitrophenyl oligosilsesquioxane and a Tn cyclo-ladder-shaped nitrophenyl oligosilsesquioxane; when the nitrophenyl oligosilsesquioxane is the T8 cage-shaped nitrophenyl oligosilsesquioxane, the obtained aminophenyl oligosilsesquioxane is a T8 cage-shaped aminophenyl oligosilsesquioxane having a structure shown in formula I; when the nitrophenyl oligosilsesquioxane is the T12 cage-shaped nitrophenyl oligosilsesquioxane, the obtained aminophenyl oligosilsesquioxane is a T12 cage-shaped aminophenyl oligosilsesquioxane having a structure shown in formula II; and when the nitrophenyl oligosilsesquioxane is the Tn cyclo-ladder-shaped nitrophenyl oligosilsesquioxane, the obtained aminophenyl oligosilsesquioxane is a Tn cyclo-ladder-shaped aminophenyl oligosilsesquioxane having a structure shown in formula III; wherein in formula I, each R is independently a phenyl or an aminophenyl, and at least one R is an aminophenyl; in formula II, each R is independently a phenyl or an aminophenyl, and at least one R is an aminophenyl; and in formula III, n≥2 and n is an integer, each R is independently a phenyl or an aminophenyl, and at least one R is an aminophenyl. The diboron compound comprises at least one of tetrahydroxydiboron, neopentyl glycol borate, pinacol borate and bispinacol resorcinol borate; and the molar ratio of the nitro functional group of the nitrophenyl oligosilsesquioxane to the reducing agent is 1:1-6. The ratio of the nitrophenyl oligosilsesquioxane to the solvent is 1g:1-40mL. The inert atmosphere comprises at least one of nitrogen and argon. 5.The aminophenyl oligosilsesquioxane prepared by the method according to any one of claims 1-4. 6.The aminophenyl oligosilsesquioxane according to claim 5, used in a polymer material. Formula I; Formula II; Formula III; 7.A polymer material, comprising the aminophenyl oligosilsesquioxane according to claim 6 and a polymer matrix; and the polymer matrix comprises at least one of an epoxy resin and a polyimide. ​ ​ 2. The production method according to claim 1, characterized by, ​ 3. The preparation method according to claim 1, characterized in that, ​ 4. The method of claim 1, wherein, ​ ​ ​ ​

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