A carborane-terminated borosilacyclane resin polymer and a method of making the same

Abstract

The application discloses a carborane-terminated borosilicon acetylene resin and a preparation method thereof. Specifically, the carborane-terminated borosilicon acetylene resin has the following structure, wherein R1 and R2 are independently H, C1-C3 alkyl, phenyl or vinyl, and n is an integer of 10-50. The carborane-terminated borosilicon acetylene resin is prepared by introducing a carborane structure to the borosilicon acetylene resin through a Grignard reagent method, and the heat resistance and the heat oxidation resistance of the resin are improved, so that the resin can be widely applied in the fields of aviation, aerospace and electronics.

Description

Technical Field

[0001] This invention belongs to the field of resin synthesis, specifically relating to a carborane-terminated borosilicate resin polymer and its preparation method. Background Technology

[0002] Since the 20th century, the rapid development of resin polymer materials has led to an expansion of their application fields and a rapid increase in usage compared to traditional metal materials. Various industries are demanding increasingly higher performance from resin materials. Therefore, to obtain high-temperature resistant resin materials with better performance and easier production, it is necessary not only to continuously improve the performance of existing resins but also to research and develop more new materials to enhance resin properties. The heat resistance temperature of traditional organic high-temperature resistant resins is affected by molecular bond energy, making it difficult for composite materials prepared from them to achieve a long-term operating temperature exceeding 450℃. Introducing inorganic elements can significantly improve the heat resistance and mechanical properties of resin materials.

[0003] Silkyne resin is a thermosetting, high-temperature resistant resin whose structure contains repeating units composed of silicon atoms linked to alkynyl groups. A typical example is borosilicate resin. After high-temperature curing, the alkynyl groups cross-link to form a network containing numerous benzene and naphthalene rings, exhibiting excellent temperature resistance. Inorganic silicon undergoes a ceramicization reaction at high temperatures, forming a dense protective layer. Furthermore, no small molecules are generated during the curing process, resulting in a dense structure.

[0004] Therefore, there is an urgent need in the field to develop inorganic silyl yne-based resins with superior performance. Summary of the Invention

[0005] One object of the present invention is to provide a carborane-terminated borosilicate resin polymer.

[0006] Another object of the present invention is to provide a method for preparing a carborane-terminated borosilicate resin polymer.

[0007] In a first aspect of the present invention, a carborane-terminated borosilicate resin is provided, the carborane-terminated borosilicate resin having the following structure:

[0008]

[0009] Wherein, R1 and R2 are each independently H, C1-C3 alkyl, phenyl or vinyl, and n is an integer from 10 to 50.

[0010] In another preferred embodiment, the molar ratio of boron to silicon in the carborane-terminated borosilicate resin is 4 / 5 to 4 / 9.

[0011] In a second aspect of the present invention, a method for preparing the carborane-terminated borosilicate resin described in the first aspect of the present invention is provided, comprising the following steps:

[0012]

[0013] (1) Under inert gas protection, at 25℃±5℃, magnesium, iodine and organic solvent are mixed, bromoethane is added, and the mixture is reacted at 55-70℃ for 1.5h~3.5h to obtain bromoethane Grignard reagent; magnesium, iodine and organic solvent are mixed, 1-bromomethylo-carborane is added, and the mixture is reacted at 55-70℃ for 1.5h~3.5h to obtain 1-bromomethylo-carborane Grignard reagent;

[0014] (2) Add m-diethynylbenzene dropwise to the bromoethane Grignard reagent obtained in step (1) and react at 55-70℃ for 2-4 hours to obtain m-diethynylbenzene Grignard reagent;

[0015] (3) Add the 1-bromomethylo-carborane reagent obtained in step (1) to the m-diethynylbenzene reagent obtained in step (2); then add dichlorosilane and react at 55-70℃ for 1.5-3.5 h to obtain the carborane-terminated borosilyne resin.

[0016] In another preferred embodiment, the bromoethane is added in the form of a solution of bromoethane in an inert solvent.

[0017] In another preferred embodiment, the bromoethane Grignard reagent is prepared and used immediately.

[0018] In another preferred embodiment, the 1-bromomethylo-ortho-carborane Grignard reagent is prepared and used immediately.

[0019] In another preferred embodiment, the 1-bromomethylo-carborane is added in the form of a solution of 1-bromomethylo-carborane in an inert solvent.

[0020] In another preferred embodiment, the m-diethynylbenzene is added in the form of a solution of m-diethynylbenzene in an inert solvent.

[0021] In another preferred embodiment, the inert solvent is an ether solvent, preferably tetrahydrofuran.

[0022] In another preferred embodiment, the method further includes a post-processing step:

[0023] After the reaction is complete, dilute hydrochloric acid solution is added to the reaction solution. After separation, the organic layer is concentrated to obtain carborane-terminated borosilicate resin.

[0024] In another preferred embodiment, the post-processing includes: after the reaction is completed, adding dilute hydrochloric acid solution to the reaction solution until it becomes acidic, filtering, separating the filtrate, drying and concentrating the organic layer to obtain a crude carborane alkyl silyne resin product, and recrystallizing it with ethanol to obtain a carborane-terminated borosilicate resin.

[0025] In another preferred embodiment, the post-treatment includes: after the reaction is completed, adding dilute hydrochloric acid to the reaction solution and stirring for 1-2 hours until the solution is acidic; filtering out the insoluble solids; adding deionized water until the solution is nearly neutral; allowing it to stand and separate into layers; adding anhydrous magnesium sulfate to the organic phase and drying; filtering to obtain a dried oil layer; rotary evaporating the residual THF to obtain a powdered solid; washing with alcohol multiple times and then vacuum drying to obtain the final product, namely carborane-terminated borosilicate resin.

[0026] In another preferred embodiment, step (1) includes the following steps: under inert gas protection, at 25℃±5℃, magnesium, iodine and organic solvent are mixed, and bromoethane is added dropwise with stirring for 0.5 to 1 h, with the temperature controlled at 25℃±5℃ during the addition. After the addition is completed, the mixture is reacted at 55-70℃ for 1.5 to 3.5 h to obtain a bromoethane Grignard reagent; magnesium, iodine and organic solvent are mixed, and 1-bromomethylo-carborane is added dropwise with stirring for 0.5 to 1 h, with the temperature controlled at 25℃±5℃ during the addition. After the addition is completed, the mixture is reacted at 55-70℃ for 1.5 to 3.5 h to obtain a 1-bromomethylo-carborane Grignard reagent. After the reaction is completed, the mixture is cooled to room temperature.

[0027] In another preferred embodiment, step (2) includes the following steps: adding m-diethynylbenzene dropwise to the bromoethane Grignard reagent obtained in step (1) for 0.5 to 1 hour, controlling the temperature at 30 to 40°C during the dropwise addition process, reacting at 55 to 70°C for 2 to 4 hours to obtain the m-diethynylbenzene Grignard reagent, and cooling to room temperature after the reaction is completed.

[0028] In another preferred embodiment, in step (1), the molar ratio of bromoethane to magnesium is 1:(1-1.5), more preferably 1:1.1; and / or

[0029] The molar ratio of 1-bromomethylo-carborane to magnesium is 1:(1 to 1.5), preferably 1:1.25.

[0030] In another preferred embodiment, the reaction time in step (1) is 1.5h to 2h.

[0031] In another preferred embodiment, the reaction time in step (2) is 1.5h to 2.5h.

[0032] In another preferred embodiment, the reaction time in step (3) is 1.5h to 2.5h.

[0033] In another preferred embodiment, the molar ratio of dichlorosilane, 1-bromomethylo-carborane, and m-diethynylbenzene is 1:(0.1-0.8):(1-0.7), more preferably 1:(0.3-0.5):(0.9-0.8).

[0034] In another preferred embodiment, step (3) includes the following steps: using a flow guide device, the 1-bromomethyl o-carborane reagent obtained in step (1) is dripped into the m-diethynylbenzene reagent obtained in step (2) by air pressure; dichlorosilane is dripped in for 0.5 to 1 hour, the temperature is controlled at 30 to 40°C during the dripping process, and then the reaction is carried out at 55 to 70°C for 1.5 to 3.5 hours to obtain the carborane-terminated borosilyne resin, and then cooled to room temperature after the reaction.

[0035] In another preferred embodiment, the dichlorosilane is added in the form of a solution of dichlorosilane in an inert solvent.

[0036] In a third aspect of the invention, a carborane-terminated borosilicate resin polymer is provided, wherein the cured product is obtained by curing the carborane-terminated borosilicate resin described in the first aspect of the invention.

[0037] In another preferred embodiment, the curing refers to temperature gradient curing.

[0038] In another preferred embodiment, the temperature gradient refers to 150℃ / 2h+200℃ / 2h+250℃ / 2h+300℃ / 2h.

[0039] In another preferred embodiment, the Td5 of the cured material is 626-661°C in a nitrogen atmosphere and 590-615°C in an air atmosphere.

[0040] In another preferred embodiment, the cured product has a mass retention rate of 89.65-91.91% at 1000°C under a nitrogen atmosphere and a mass retention rate of 51.27-91.13% under an air atmosphere.

[0041] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here. Attached Figure Description

[0042] Figure 1 The infrared spectrum of the methylhydrocarbonboryl alkylborane silyldiyne prepared in Example 1 is shown.

[0043] Figure 2 The TGA spectrum of the methylhydrocarbonboryl alkylborosilicate prepared in Example 1 is shown.

[0044] Figure 3 The infrared spectrum of the dimethylcarboalkylboranesilyne prepared in Example 2 is shown.

[0045] Figure 4 The TGA spectrum of the dimethylcarboalkylborosilicate prepared in Example 2 is shown.

[0046] Figure 5 The infrared spectrum of the methylvinylcarborylalkylborosilicate prepared in Example 3 is shown.

[0047] Figure 6 The TGA spectrum of the methylvinylcarborylalkylborosilicate prepared in Example 3 is shown. Detailed Implementation

[0048] Through extensive and in-depth research, the inventors have provided a novel carborane-terminated borosilicate resin polymer. The carborane structure is introduced to end the borosilicate resin using the Grignard reagent method. By controlling the feed ratio, the molecular weight and the silicon-boron element ratio are adjusted, thereby regulating the high-temperature resistance and heat oxidation resistance of the borosilicate resin. Based on this, the inventors have completed this invention.

[0049] Carborane-terminated borosilicate resin polymers and their preparation methods

[0050] Carboranes are a class of three-dimensional σ-aromatic cage-like atomic groups with unique electronic effects and large steric hindrance, exhibiting good chemical and thermal stability. Based on these advantages, carboranes have attracted considerable attention in many fields, such as organic materials chemistry, organometallic chemistry, medicinal chemistry, mechanochemistry, and boron neutron capture therapy.

[0051] This invention introduces a carborane structure to cap borosilicate resin using the Grignard reagent method. By controlling the feed ratio, molecular weight and the silicon-boron element ratio can be adjusted, thus achieving the goal of molecular design. The introduction of the carborane structure increases the inorganic element content in the borosilicate resin, further improving its high-temperature resistance and heat oxidation resistance, and showing broad application prospects in the fields of high-temperature resins and ceramic precursors.

[0052] Specifically, the carborane-terminated borosiyne resin polymer provided by the present invention has the following structure:

[0053]

[0054] Wherein, R1 and R2 are each independently H, C1-C3 alkyl, phenyl or vinyl, and n is an integer from 10 to 50.

[0055] In particular, this invention discovers that the molecular weight and silicon-boron ratio of carborane-terminated borosilicate resin can be controlled by adjusting the raw material feeding ratio. Specifically, the higher the boron content, the more significant the improvement in the heat resistance and oxidation resistance of the carborane-terminated borosilicate resin.

[0056] Typically, the preparation process of the compounds of the present invention is as shown in the embodiments of the present invention, wherein the raw materials and reagents used can be purchased commercially unless otherwise specified.

[0057] The carborane-terminated borosilicate resin of the present invention is prepared by reacting magnesium powder, bromoethane, dichlorosilane, and 1-bromomethylo-carborane in four steps: the first step is to prepare bromoethane Grignard reagent and 1-bromomethylo-carborane Grignard reagent by reacting magnesium powder with bromoethane and 1-bromomethylo-carborane respectively; the second step is to add m-diethynylbenzene to the bromoethane Grignard reagent obtained in the first step to obtain an ethynyl Grignard reagent; the third step is to mix the Grignard reagent obtained in the second step with the 1-bromomethylcarborane Grignard reagent and react it with dichlorosilane to obtain a crude product; the fourth step is to post-process the crude product to obtain the final product.

[0058] By adjusting the ratio of m-diethynylbenzene and 1-bromomethylo-carborane, the proportion of inorganic elements in the polymer structure can be controlled, thus achieving controllable polymer molecular weight and properties. The carborane-terminated borosilicate resin polymer prepared by this invention is readily soluble in common low-boiling-point organic solvents, exhibits excellent heat resistance, and can be widely used in aerospace, electronic packaging, ceramic precursors, and other fields.

[0059] Specifically, the preparation method of the present invention is as follows:

[0060]

[0061] (1) Under inert gas protection, magnesium powder and iodine were added to two four-necked flasks respectively, using tetrahydrofuran as solvent, and stirred at high speed at 20℃~25℃. Then, bromoethane / THF solution and 1-bromomethylo-carborane / THF solution were added dropwise to the two flasks respectively using a constant pressure funnel. The addition time was 0.5~1h, and the temperature was controlled at 25℃±5℃ during the addition. After the addition was completed, the temperature was raised to 63℃ and the reaction was allowed to proceed for 1.5h~2.5h to obtain bromoethane Grignard reagent and 1-bromomethylo-carborane Grignard reagent. After the reaction was completed, the mixture was cooled to room temperature.

[0062] (2) Add m-diethynylbenzene / THF solution dropwise to the bromoethane Grignard reagent using a constant pressure funnel for 0.5 to 1 hour. Control the temperature at 30 to 40°C during the dropwise addition. After the dropwise addition is complete, raise the temperature to 63°C and react for 2 to 4 hours to obtain the m-diethynylbenzene Grignard reagent. After the reaction is complete, cool to room temperature.

[0063] (3) In the second step reaction, the 1-bromomethylo-carborane Grignard reagent prepared in the first step is mixed and added dropwise using a flow guide device and gas pressure. Then, dichlorosilane / THF solution is added dropwise in a constant pressure funnel for 0.5 to 1 hour. The temperature is controlled at 30 to 40°C during the addition process. After the addition is completed, the temperature is raised to 63°C and reacted for 1.5 to 3.5 hours. After the reaction, the temperature is cooled to room temperature.

[0064] (4) Add dilute hydrochloric acid dropwise to the reaction solution and stir for 1-2 hours until the solution becomes acidic. Filter out the insoluble solids, add deionized water until the solution is nearly neutral, let stand to separate the layers, and use a separatory funnel to separate the oil layer. Add anhydrous magnesium sulfate and let it dry overnight. Filter to obtain the dried oil layer, rotary evaporate the residual THF to obtain a powdery solid, wash with alcohol several times, and then vacuum dry to obtain the final product.

[0065] The inert gas mentioned is a common inert gas in the art, including but not limited to nitrogen and argon.

[0066] Compared with the prior art, the main advantages of the present invention include:

[0067] (1) The present invention prepared carborane-terminated borosilicate resin by Grignard reagent method. The molecular chain length and inorganic borosilicate content ratio were adjusted by adjusting the feed ratio of raw materials. The molecular designability was good, the content of inorganic elements in the resin matrix was increased, and the temperature resistance and heat oxidation resistance of the resin were improved.

[0068] (2) The carborane-terminated borosilicate resin of the present invention has good processing performance, can be dissolved in conventional low-boiling point solvents, is suitable for a variety of processing technologies, and can be used to prepare various high-performance composite materials.

[0069] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

[0070] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this invention. The preferred embodiments and materials described herein are for illustrative purposes only.

[0071] Example 1

[0072] Preparation steps of carborane-terminated methylborosilicate resin:

[0073] Under anhydrous and oxygen-free conditions, 0.2 mol of magnesium powder, 0.01 g of iodine, and 40 g of THF were added to a four-necked flask and stirred at high speed. 0.18 mol of bromoethane was dissolved in 40 g of THF and slowly added dropwise through a constant-pressure funnel, maintaining a temperature of 25 °C ± 5 °C. After the addition was complete, the temperature was raised to 63 °C, refluxed for 1.5 h, and then cooled to room temperature. 0.08 mol of m-diethynylbenzene was dissolved in 20 g of THF and slowly added dropwise through a constant-pressure funnel, maintaining a temperature of 30–40 °C. After the addition was complete, the temperature was raised to 63 °C, refluxed for 2 h, and then cooled to room temperature.

[0074] Under anhydrous and oxygen-free conditions, 0.05 mol magnesium powder, 0.01 g iodine, and 15 g THF were added to a four-necked flask and stirred magnetically. 0.04 mol 1-bromomethyl o-carborane was dissolved in 15 g THF and slowly added dropwise through a constant pressure funnel while maintaining a temperature of 25℃±5℃. After the addition was complete, the temperature was raised to 63℃, refluxed for 1.5 h, and then cooled to room temperature.

[0075] Using a flow guide device, the 1-bromomethylo-carborane Grignard reagent was mixed and added dropwise to the above reaction system under pressure. 0.09 mol of methyldichlorosilane was dissolved in 30 g of THF and slowly added dropwise to the mixed Grignard reagent system through a constant pressure funnel, with the temperature controlled at 30–40 °C. After the addition was complete, the temperature was raised to 63 °C and refluxed for 2 h.

[0076] Dilute hydrochloric acid was added dropwise to the reaction solution and stirred for 1 hour until the solution became acidic. After filtering out the insoluble solids, deionized water was added until the solution was nearly neutral. The mixture was allowed to stand and separate into layers. The oil layer was obtained by separating the layers using a separatory funnel. Anhydrous magnesium sulfate was added and the mixture was left to dry overnight. The dried oil layer was obtained by vacuum filtration. The residual THF was removed by rotary evaporation to obtain a powdery solid. After repeated alcohol washing, the solid was dried under vacuum to obtain the final product.

[0077] The resin was cured in a muffle furnace by stepwise temperature increases at the following conditions: 150℃ / 2h + 200℃ / 2h + 250℃ / 2h + 300℃ / 2h.

[0078] Example 2

[0079] Preparation steps of carborane-terminated dimethylborosilicate resin:

[0080] Under anhydrous and oxygen-free conditions, 0.2 mol of magnesium powder, 0.01 g of iodine, and 20 g of THF were added to a four-necked flask and stirred at high speed. 0.18 mol of bromoethane was dissolved in 60 g of THF and slowly added dropwise through a constant-pressure funnel at a controlled temperature of 25 °C ± 5 °C. After the addition was complete, the temperature was raised to 63 °C, refluxed for 1.5 h, and then cooled to room temperature. 0.09 mol of m-diethynylbenzene was dissolved in 25 g of THF and slowly added dropwise through a constant-pressure funnel at a controlled temperature of 30–40 °C. After the addition was complete, the temperature was raised to 63 °C, refluxed for 2.5 h, and then cooled to room temperature.

[0081] Under anhydrous and oxygen-free conditions, 0.04 mol magnesium powder, 0.01 g iodine, and 20 g THF were added to a four-necked flask and stirred magnetically. 0.03 mol 1-bromomethylcarborane was dissolved in 15 g THF and slowly added dropwise through a constant pressure funnel while maintaining a temperature of 25℃±5℃. After the addition was complete, the temperature was raised to 63℃, refluxed for 2 hours, and then cooled to room temperature.

[0082] Using a flow guide device, the 1-bromomethylo-carborane Grignard reagent was mixed and added dropwise to the above reaction system under pressure. 0.09 mol of dimethyldichlorosilane was dissolved in 40 g of THF and slowly added dropwise to the mixed Grignard reagent system through a constant pressure funnel, with the temperature controlled at 30–40 °C. After the addition was complete, the temperature was raised to 63 °C and refluxed for 1.5 h.

[0083] Dilute hydrochloric acid was added dropwise to the reaction solution and stirred for 1.5 hours until the solution became acidic. After filtering out the insoluble solids, deionized water was added until the solution was nearly neutral. The mixture was allowed to stand and separate into layers. The oil layer was obtained by separating the layers using a separatory funnel. Anhydrous magnesium sulfate was added and the mixture was left to dry overnight. The dried oil layer was obtained by vacuum filtration. The residual THF was removed by rotary evaporation to obtain a powdery solid. After repeated alcohol washing, the solid was dried under vacuum to obtain the final product.

[0084] The resin was cured in a muffle furnace by stepwise temperature increases at the following conditions: 150℃ / 2h + 200℃ / 2h + 250℃ / 2h + 300℃ / 2h.

[0085] Example 3

[0086] Preparation steps of carborane-terminated methylvinylborosilicate resin:

[0087] Under anhydrous and oxygen-free conditions, 0.2 mol of magnesium powder, 0.01 g of iodine, and 30 g of THF were added to a four-necked flask and stirred at high speed. 0.18 mol of bromoethane was dissolved in 50 g of THF and slowly added dropwise through a constant-pressure funnel at a controlled temperature of 25 °C ± 5 °C. After the addition was complete, the temperature was raised to 63 °C, refluxed for 1.5 h, and then cooled to room temperature. 0.085 mol of m-diethynylbenzene was dissolved in 25 g of THF and slowly added dropwise through a constant-pressure funnel at a controlled temperature of 30–40 °C. After the addition was complete, the temperature was raised to 63 °C, refluxed for 2.5 h, and then cooled to room temperature.

[0088] Under anhydrous and oxygen-free conditions, 0.05 mol magnesium powder, 0.01 g iodine, and 15 g THF were added to a four-necked flask and stirred magnetically. 0.035 mol 1-bromomethylcarborane was dissolved in 10 g THF and slowly added dropwise through a constant pressure funnel while maintaining a temperature of 25℃±5℃. After the addition was complete, the temperature was raised to 63℃, refluxed for 1.5 h, and then cooled to room temperature.

[0089] Using a flow guide device, the 1-bromomethylo-carborane Grignard reagent was mixed and added dropwise to the above reaction system under pressure. 0.1 mol of methylvinyldichlorosilane was dissolved in 40 g of THF and slowly added dropwise to the mixed Grignard reagent system through a constant pressure funnel, with the temperature controlled at 30–40 °C. After the addition was complete, the temperature was raised to 63 °C and refluxed for 2.5 h.

[0090] Dilute hydrochloric acid was added dropwise to the reaction solution and stirred for 1.5 hours until the solution became acidic. After filtering out the insoluble solids, deionized water was added until the solution was nearly neutral. The mixture was allowed to stand and separate into layers. The oil layer was obtained by separating the layers using a separatory funnel. Anhydrous magnesium sulfate was added and the mixture was left to dry overnight. The dried oil layer was obtained by vacuum filtration. The residual THF was removed by rotary evaporation to obtain a powdery solid. After repeated alcohol washing, the solid was dried under vacuum to obtain the final product.

[0091] The resin was cured in a muffle furnace by stepwise temperature increases at the following conditions: 150℃ / 2h + 200℃ / 2h + 250℃ / 2h + 300℃ / 2h.

[0092] Comparative Example 1

[0093] Under anhydrous and oxygen-free conditions, 2.4 g of magnesium shavings and 0.01 g of iodine granules were added to a flask, and 20 g of THF solvent was added dropwise through a constant-pressure funnel while stirring at a constant speed. 10.36 g of bromoethane and 50 g of THF were mixed and added dropwise through a constant-pressure funnel, with the temperature controlled at 25℃ ± 5℃. After the addition was complete, the temperature was raised to 63℃ and refluxed for 1.5 h. After cooling, a mixed solution of 5.67 g of m-diethynylbenzene and 20 g of THF was added to the constant-pressure funnel, and the mixture was added slowly, followed by further heating to 63℃ and refluxing for 2 h. After cooling to room temperature, 0.04 mol of dimethyldichlorosilane monomer and 20 g of THF were added, and the temperature was raised again to 63℃ and refluxed for 1.5 h after the addition was complete.

[0094] Add 50g of 5% hydrochloric acid to the solution obtained in the previous step, stir at room temperature for 30 minutes, then remove, filter, wash with water, separate, dry, filter again, and rotary evaporate to finally obtain poly(m-diethynylbenzene-dimethylsilane) resin.

[0095] The resin was cured in a muffle furnace by stepwise temperature increases: 150℃ / 2h + 200℃ / 2h + 250℃ / 2h + 300℃ / 2h + 350℃ / 2h.

[0096] The cured products from the examples were subjected to TGA tests in nitrogen and air atmospheres at a heating rate of 10°C / min. The thermal decomposition temperature (Td5) with a 5% mass loss and the mass retention rate at 1000°C are shown in the table below:

[0097]

[0098] As can be seen from the table above, the high-temperature resistance and heat oxidation resistance of the carborane-terminated borosilicate resin of the present invention are significantly improved after the introduction of carborane.

[0099] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A carborane-terminated borosilacyclopene resin, characterized by, The carbon borane-terminated borosilacycle resin has the following structure: wherein R1 and R2 are each independently H, C1-C3 alkyl, phenyl or vinyl, and n is an integer of 10-50.

2. A method of preparing the carborane-terminated borosilicon acetylene resin of claim 1, characterized by, The method comprises the following steps: (1) under the protection of inert gas, at 25℃±5℃, mixing magnesium, iodine and organic solvent, adding bromoethane, and reacting at 55-70℃ for 1.5-3.5h to obtain a bromoethane format reagent; mixing magnesium, iodine and organic solvent, adding 1-bromomethyl ortho-carborane, and reacting at 55-70℃ for 1.5-3.5h to obtain a 1-bromomethyl ortho-carborane format reagent; (2) adding m-diethynylbenzene dropwise to the bromoethane format reagent obtained in step (1) and reacting at 55-70℃ for 2-4h to obtain a m-diethynylbenzene format reagent; (3) adding the 1-bromomethyl ortho-carborane format reagent obtained in step (1) dropwise to the m-diethynylbenzene format reagent obtained in step (2), then adding dichlorosilane dropwise, and reacting at 55-70℃ for 1.5-3.5h to obtain the carbon borane-terminated borosilacycle resin; wherein the molar ratio of dichlorosilane, 1-bromomethyl ortho-carborane and m-diethynylbenzene is 1:(0.3-0.5):(0.8-1).

3. The production method according to claim 2, wherein The method further comprises a post-treatment step: After the reaction is completed, dilute hydrochloric acid solution is added to the reaction solution, the organic layer is concentrated after being separated, and the carbon borane-terminated borosilacycle resin is obtained.

4. The production method according to claim 2, wherein In step (1), the molar ratio of bromoethane and magnesium is 1:(1-1.5); and / or The molar ratio of 1-bromomethyl ortho-carborane and magnesium is 1:(1-1.5).

5. The production method according to claim 2, wherein In step (1), the molar ratio of bromoethane and magnesium is 1:1.1; and / or The molar ratio of 1-bromomethyl ortho-carborane and magnesium is 1:1.

25.

6. The production method according to claim 2, wherein In step (1), the reaction time is 1.5-2h.

7. The production method according to claim 2, wherein In step (2), the reaction time is 1.5-2.5h.

8. The production method according to claim 2, wherein In step (3), the reaction time is 1.5-2.5h.

9. The production method according to claim 2, wherein Step (3) comprises the following steps: using air pressure to drop the 1-bromomethyl ortho-carborane format reagent obtained in step (1) into the m-diethynylbenzene format reagent obtained in step (2) through a flow guide device; adding dichlorosilane dropwise, the dropwise adding time being 0.5-1h, the temperature being controlled at 30-40℃ during the dropwise adding process, and then reacting at 55-70℃ for 1.5-3.5h to obtain the carbon borane-terminated borosilacycle resin, and cooling to room temperature after the reaction.

10. A carbonborane-terminated borosilacycine resin cured product, characterized by, The cured product is obtained by curing the carbon borane-terminated borosilacycle resin according to claim 1.

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