Carborane-terminated borosilicate alkyne resin polymer and preparation method thereof

Abstract

The invention discloses carborane-terminated boron-silicon-alkyne resin and a preparation method of the carborane-terminated boron-silicon-alkyne resin. Specifically, the carborane-terminated boron-silicon-alkyne resin has the following structure, R1 and R2 are respectively and independently H, C1-C3 alkyl, phenyl or vinyl, and n is an integer of 10-50. A carborane structure is introduced through a Grignard reagent method to terminate the borosilicate alkyne resin, so that the heat resistance and thermal oxidation resistance of the resin are improved, and the resin can be widely applied to the fields of aerospace, electronics and the like. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of resin synthesis, and in particular relates to a carborane-terminated borosilicate resin polymer and a preparation method thereof. Background Art

[0002] Since the 20th century, resin polymer materials have developed rapidly, their application fields have continued to expand, and their usage has quickly exceeded that of traditional metal materials. Various industries have increasingly higher requirements for the performance of resin materials. Therefore, in order 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 improve resin performance. The heat-resistant temperature of traditional organic high-temperature resistant resins is affected by the molecular bond energy, which makes it difficult for the long-term working temperature of the composite materials prepared by them to exceed 450°C. The introduction of inorganic elements can greatly improve the heat resistance and mechanical properties of resin materials.

[0003] Silicylidene resin refers to a thermosetting high-temperature resistant resin that contains repeating units consisting of silicon atoms and acetylenes in the resin structure, of which borosilicate resin is a typical example. After high-temperature curing, the acetylenes will cross-link with each other to form a network containing a large number of benzene rings and naphthalene rings, with excellent heat resistance. The inorganic silicon element will undergo a ceramic reaction at high temperatures to form a dense protective layer, and no small molecules will be generated during the curing process, with a dense structure.

[0004] In view of this, there is an urgent need in the art to develop inorganic silane-based resins with better performance. Summary of the invention

[0005] An 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, wherein the carborane-terminated borosilicate resin has the following structure:

[0008]

[0009] Among them, R 1 and R 2 Each is 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 / 51-4 / 9.

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

[0012]

[0013] (1) Under the protection of inert gas, at 25°C ± 5°C, magnesium, iodine and an organic solvent are mixed, ethyl bromide is added, and the mixture is reacted at 55-70°C for 1.5 hours to 3.5 hours to obtain an ethyl bromide Grignard reagent; magnesium, iodine and an organic solvent are mixed, 1-bromomethyl-o-carborane is added, and the mixture is reacted at 55-70°C for 1.5 hours to 3.5 hours to obtain a 1-bromomethyl-o-carborane Grignard reagent;

[0014] (2) adding m-diethynylbenzene dropwise to the bromoethane Grignard reagent obtained in step (1), and reacting at 55-70° C. for 2-4 hours to obtain m-diethynylbenzene Grignard reagent;

[0015] (3) Add the 1-bromomethyl-o-carborane Grignard reagent obtained in step (1) dropwise into the m-diethynylbenzene Grignard reagent obtained in step (2); then add dichlorosilane dropwise, and react at 55-70° C. for 1.5-3.5 hours to obtain the carborane-terminated borosilicate resin.

[0016] In another preferred embodiment, the ethyl bromide is added in the form of a solution of ethyl bromide 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-bromomethyl o-carborane Grignard reagent is prepared and used immediately.

[0019] In another preferred embodiment, the 1-bromomethyl-o-carborane is added in the form of a solution of 1-bromomethyl-o-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 comprises a post-processing step:

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

[0024] In another preferred embodiment, the post-treatment includes: after the reaction is completed, adding dilute hydrochloric acid solution to the reaction solution to make it acidic, filtering, separating the filtrate, drying and concentrating the organic layer to obtain a crude product of the carborane silane resin, and recrystallizing from ethanol to obtain a carborane-terminated borosilane 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 to 2 hours until the solution is acidic, filtering out insoluble solids, adding deionized water until the solution is close to neutral, standing to separate the layers, adding anhydrous magnesium sulfate to the organic phase for drying; filtering to obtain a dry 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, i.e., carborane-terminated borosilicate resin.

[0026] In another preferred embodiment, step (1) comprises the following steps: under the protection of inert gas, at 25°C±5°C, mixing magnesium, iodine and an organic solvent, adding bromoethane dropwise while stirring, the dropping time is 0.5 to 1h, the temperature is controlled at 25°C±5°C during the dropping process, and the reaction is carried out at 55-70°C for 1.5h to 3.5h after the dropping is completed to obtain bromoethane Grignard reagent; mixing magnesium, iodine and an organic solvent, adding 1-bromomethyl-o-carborane dropwise while stirring, the dropping time is 0.5 to 1h, the temperature is controlled at 25°C±5°C during the dropping process, and the reaction is carried out at 55-70°C for 1.5h to 3.5h after the dropping is completed to obtain 1-bromomethyl-o-carborane Grignard reagent, and cooling to room temperature after the reaction is completed.

[0027] In another preferred embodiment, step (2) comprises the following steps: adding m-diethynylbenzene dropwise to the bromoethane Grignard reagent obtained in step (1), the dropping time being 0.5 to 1 h, controlling the temperature at 30 to 40° C. during the dropping process, reacting at 55 to 70° C. for 2 to 4 h to obtain 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 ethyl bromide to magnesium is 1:(1-1.5), preferably 1:1.1; and / or

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

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

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

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

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

[0034] In another preferred embodiment, step (3) comprises the following steps: dripping the 1-bromomethyl-o-carborane Grignard reagent obtained in step (1) into the m-diethynylbenzene Grignard reagent obtained in step (2) by using air pressure through a flow guide device; dripping dichlorosilane for 0.5 to 1 h, controlling the temperature at 30 to 40° C. during the dripping process, and then reacting at 55 to 70° C. for 1.5 to 3.5 h to obtain the carborane-terminated borosilicate resin, and cooling 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 present 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 present 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 solidified material in a nitrogen atmosphere is 626-661°C; and the Td5 in an air atmosphere is 590-615°C.

[0040] In another preferred embodiment, the mass retention rate of the solidified material at 1000° C. in a nitrogen atmosphere is 89.65-91.91%; and the mass retention rate in an air atmosphere is 51.27-91.13%.

[0041] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (such as embodiments) can be combined with each other to form a new or preferred technical solution. Due to space limitations, they will not be described one by one here. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is the infrared spectrum of the methyl hydrogen carborane silyl borohydride prepared in Example 1.

[0043] Figure 2 This is the TGA spectrum of the methyl hydrogen carborane borosilylene prepared in Example 1.

[0044] Figure 3 This is the infrared spectrum of the dimethylcarboryl borosilicate prepared in Example 2.

[0045] Figure 4 This is the TGA spectrum of the dimethylcarboryl borosilicate prepared in Example 2.

[0046] Figure 5 This is the infrared spectrum of the methylvinyl carborane silyl borohydride prepared in Example 3.

[0047] Figure 6 This is the TGA spectrum of the methylvinyl carborane borosilicate prepared in Example 3. DETAILED DESCRIPTION

[0048] After extensive and in-depth research, the inventors have provided a borosilicate resin polymer with a completely new structure capped with carborane. The borosilicate resin is capped by introducing a carborane structure through a Grignard reagent method, and the molecular weight is controlled and the ratio of silicon and boron elements is adjusted by controlling the feed ratio, thereby regulating the high temperature resistance and thermal oxidation resistance of the borosilicate resin. Based on this, the inventors have completed the present invention.

[0049] Carborane-terminated borosilicate resin polymer and preparation method thereof

[0050] Carborane is a three-dimensional σ-aromatic cage-like atomic group with special electronic effects and large volume steric hindrance, which has good chemical and thermal stability. Based on these advantages, carborane has received great attention in many fields, such as organic material chemistry, metal organic chemistry, medicinal chemistry, mechanochemistry and boron neutron capture therapy.

[0051] The present invention introduces a carborane structure through a Grignard reagent method to end-cap the borosilicate resin, and can achieve molecular weight control and adjustment of the silicon-boron element ratio by controlling the feed ratio, thereby achieving the purpose of molecular design. The introduction of the carborane structure increases the content of inorganic elements in the borosilicate resin, and can further improve the high temperature resistance and thermal oxidation resistance of the borosilicate resin, and has broad application prospects in the fields of high temperature resistant resins and ceramic precursors.

[0052] Specifically, the carborane-terminated borosilicate resin polymer provided by the present invention has the structure shown below:

[0053]

[0054] Among them, R 1 and R 2 Each is independently H, C1-C3 alkyl, phenyl or vinyl, and n is an integer from 10 to 50.

[0055] In particular, the present invention finds that the molecular weight and the ratio of silicon and boron elements of the carborane-terminated borosilicate resin can be controlled by the feed ratio of the raw materials. Specifically, the higher the boron content, the more significantly the heat resistance and oxidation resistance of the carborane-terminated borosilicate resin are improved.

[0056] Typically, the process flow for preparing the compounds of the present invention is as shown in the examples of the present invention, wherein the raw materials and reagents used can be purchased through commercial channels unless otherwise specified.

[0057] The carborane-terminated borosilicate resin of the invention is prepared by using magnesium powder, ethyl bromide, dichlorosilane and 1-bromomethyl-o-carborane as raw materials through four-step reactions: in the first step, ethyl bromide Grignard reagent and 1-bromomethyl-o-carborane Grignard reagent are prepared by reacting magnesium powder with ethyl bromide and 1-bromomethyl-o-carborane respectively; in the second step, m-diethynylbenzene is added to the ethyl bromide Grignard reagent obtained in the first step to obtain an ethynyl Grignard reagent; in the third step, the Grignard reagent obtained in the second step is mixed with the 1-bromomethyl-carborane Grignard reagent and then reacted with dichlorosilane to obtain a crude product; and in the fourth step, the crude product is post-treated to obtain a product.

[0058] By adjusting the ratio of m-diethynylbenzene and 1-bromomethyl-o-carborane, the ratio of inorganic elements in the polymer structure is adjusted to achieve controllable polymer molecular weight and performance. The carborane-terminated borosilicate resin polymer prepared by the present invention is easily soluble in common low-boiling organic solvents, has 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 the protection of inert gas, magnesium powder and iodine are added to two four-necked flasks respectively, tetrahydrofuran is used as solvent, and the mixture is stirred at a high speed at 20°C to 25°C. Then, ethyl bromide / THF solution and 1-bromomethyl-o-carborane / THF solution are added dropwise to the two flasks respectively using a constant pressure funnel. The addition time is 0.5 to 1 h. During the addition, the temperature is controlled at 25°C ± 5°C. After the addition is completed, the temperature is raised to 63°C and reacted for 1.5 to 2.5 h to obtain ethyl bromide Grignard reagent and 1-bromomethyl-o-carborane Grignard reagent. After the reaction is completed, the mixture is cooled to room temperature.

[0062] (2) Add the m-diethynylbenzene / THF solution dropwise to the bromoethane Grignard reagent using a constant pressure funnel for 0.5 to 1 h. The temperature is controlled at 30 to 40° C. during the addition. After the addition is completed, the temperature is raised to 63° C. and reacted for 2 to 4 h to obtain the m-diethynylbenzene Grignard reagent. After the reaction is completed, the reaction is cooled to room temperature.

[0063] (3) The 1-bromomethyl-o-carborane Grignard reagent prepared in the first step is mixed and dripped into the m-diethynylbenzene Grignard reagent in the second step through a flow guide device using air pressure, and then a dichlorosilane / THF solution is added to a constant pressure funnel and dripped dropwise for 0.5 to 1 h. The temperature is controlled at 30 to 40° C. during the dripping process. After the dripping is completed, the temperature is raised to 63° C. for reaction for 1.5 to 3.5 h, and then cooled to room temperature after the reaction.

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

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

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

[0067] (1) The present invention prepares a carborane-terminated borosilicate resin by a Grignard reagent method, and adjusts the molecular chain length and the content ratio of inorganic boron and silicon elements by adjusting the feed ratio of the raw materials. The molecular designability is good, the content of inorganic elements in the resin matrix is ​​increased, and the temperature resistance and thermal oxidation resistance of the resin are 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 techniques, and can be used to prepare various high-performance composite materials.

[0069] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples without specifying specific conditions are usually based on conventional conditions or the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are calculated by weight.

[0070] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein can be applied to the methods of the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only.

[0071] Example 1

[0072] Preparation steps of carborane-terminated methyl hydrogen borosilane resin:

[0073] Under anhydrous and oxygen-free conditions, add 0.2 mol magnesium powder, 0.01 g iodine, and 40 g THF into a four-necked flask and stir at high speed. Dissolve 0.18 mol bromoethane in 40 g THF and slowly drip it through a constant pressure funnel. Control the temperature at 25°C ± 5°C. After the dripping is complete, heat it to 63°C, reflux for 1.5 hours, and then cool it to room temperature. Dissolve 0.08 mol m-diethynylbenzene in 20 g THF and slowly drip it through a constant pressure funnel. Control the temperature at 30-40°C. After the dripping is complete, heat it to 63°C, reflux for 2 hours, and then cool it to room temperature.

[0074] Under anhydrous and oxygen-free conditions, add 0.05 mol magnesium powder, 0.01 g iodine, and 15 g THF into a four-necked flask and stir magnetically. Dissolve 0.04 mol 1-bromomethyl-o-carborane in 15 g THF and slowly add dropwise through a constant pressure funnel. Control the temperature at 25°C ± 5°C. After the addition is complete, raise the temperature to 63°C, reflux for 1.5 h, and then cool to room temperature.

[0075] Through the flow guide device, use the air pressure to drip the 1-bromomethyl-o-carborane Grignard reagent mixture into the above reaction system. Dissolve 0.9 mol of methylhydrodichlorosilane in 30 g of THF and slowly drip it into the mixed Grignard reagent system through a constant pressure funnel, control the temperature at 30-40°C, and after the dripping is completed, heat it to 63°C and reflux for 2 hours.

[0076] Add dilute hydrochloric acid to the reaction solution and stir for 1 hour until the solution is acidic. Filter out the insoluble solids and add deionized water until the solution is close to neutral. Let stand to separate the layers. Use a separatory funnel to separate the oil layer. Add anhydrous magnesium sulfate and let it dry overnight. Filter the dried oil layer by suction, remove the residual THF by rotary evaporation to obtain a powdered solid, wash with alcohol several times and then vacuum dry to obtain the final product.

[0077] The resin was cured in a muffle furnace by step-heating at 150°C / 2h+200°C / 2h+250°C / 2h+300°C / 2h.

[0078] Example 2

[0079] Preparation steps of carborane-terminated dimethyl borosilicate resin:

[0080] Under anhydrous and oxygen-free conditions, add 0.2 mol magnesium powder, 0.01 g iodine, and 20 g THF into a four-necked flask and stir at high speed. Dissolve 0.18 mol bromoethane in 60 g THF and slowly drip it through a constant pressure funnel. Control the temperature at 25°C ± 5°C. After the dripping is complete, heat it to 63°C, reflux for 1.5 hours, and then cool it to room temperature. Dissolve 0.09 mol m-diethynylbenzene in 25 g THF and slowly drip it through a constant pressure funnel. Control the temperature at 30-40°C. After the dripping is complete, heat it to 63°C, reflux for 2.5 hours, and then cool it to room temperature.

[0081] Under anhydrous and oxygen-free conditions, add 0.04 mol magnesium powder, 0.01 g iodine, and 20 g THF into a four-necked flask and stir magnetically. Dissolve 0.03 mol 1-bromomethylcarborane in 15 g THF and slowly add dropwise through a constant pressure funnel. Control the temperature at 25°C ± 5°C. After the addition is complete, raise the temperature to 63°C, reflux for 2 h, and then cool to room temperature.

[0082] Through the flow guide device, use air pressure to drip the 1-bromomethyl-o-carborane Grignard reagent mixture into the above reaction system. Dissolve 0.9 mol of dimethyldichlorosilane in 40 g of THF and slowly drip it into the mixed Grignard reagent system through a constant pressure funnel, control the temperature at 30-40°C, and after the dripping is completed, heat it to 63°C and reflux for 1.5 hours.

[0083] Dilute hydrochloric acid was added dropwise to the reaction solution and stirred for 1.5 hours until the solution was acidic. After filtering out the insoluble solid, deionized water was added until the solution was close to neutral. The solution was allowed to stand for stratification, and the oil layer was separated using a separatory funnel. Anhydrous magnesium sulfate was added and allowed to dry overnight. The dry oil layer was filtered out by suction, and the residual THF was removed by rotary evaporation to obtain a powdery solid. After multiple alcohol washings, the final product was dried in vacuo to obtain the final product.

[0084] The resin was cured in a muffle furnace by step-heating at 150°C / 2h+200°C / 2h+250°C / 2h+300°C / 2h.

[0085] Example 3

[0086] Preparation steps of carborane terminated methyl vinyl borosilicate resin:

[0087] Under anhydrous and oxygen-free conditions, add 0.2 mol magnesium powder, 0.01 g iodine, and 30 g THF into a four-necked flask and stir at high speed. Dissolve 0.18 mol bromoethane in 50 g THF and slowly drip through a constant pressure funnel, control the temperature at 25°C ± 5°C, raise the temperature to 63°C after the addition is complete, reflux for 1.5 hours, and cool to room temperature. Dissolve 0.085 mol m-diethynylbenzene in 25 g THF and slowly drip through a constant pressure funnel, control the temperature at 30-40°C, raise the temperature to 63°C after the addition is complete, reflux for 2.5 hours, and cool to room temperature.

[0088] Under anhydrous and oxygen-free conditions, add 0.05 mol magnesium powder, 0.01 g iodine, and 15 g THF into a four-necked flask and stir magnetically. Dissolve 0.035 mol 1-bromomethylcarborane in 10 g THF and slowly add dropwise through a constant pressure funnel. Control the temperature at 25°C ± 5°C. After the addition is complete, raise the temperature to 63°C, reflux for 1.5 h, and then cool to room temperature.

[0089] Through the flow guide device, use air pressure to drip the 1-bromomethyl-o-carborane Grignard reagent mixture into the above reaction system. Dissolve 1 mol of methylvinyldichlorosilane in 40g THF and slowly drip it into the mixed Grignard reagent system through a constant pressure funnel, control the temperature at 30-40°C, raise the temperature to 63°C after the addition is completed, and reflux for 2.5h.

[0090] Dilute hydrochloric acid was added dropwise to the reaction solution and stirred for 1.5 hours until the solution was acidic. After filtering out the insoluble solid, deionized water was added until the solution was close to neutral. The solution was allowed to stand for stratification, and the oil layer was separated using a separatory funnel. Anhydrous magnesium sulfate was added and allowed to dry overnight. The dry oil layer was filtered out by suction, and the residual THF was removed by rotary evaporation to obtain a powdery solid. After multiple alcohol washings, the final product was dried in vacuo to obtain the final product.

[0091] The resin was cured in a muffle furnace by step-heating at 150°C / 2h+200°C / 2h+250°C / 2h+300°C / 2h.

[0092] Comparative Example 1

[0093] Under anhydrous and oxygen-free conditions, add 2.4g magnesium chips and 0.01g iodine particles into the flask, add 20gTHF solvent dropwise through a constant pressure funnel, and stir at a uniform speed. Take 10.36g bromoethane and 50gTHF, mix them, add dropwise through a constant pressure funnel, and control the temperature at 25℃±5℃. After the addition is complete, heat to 63℃ and reflux for 1.5h. After cooling, add 5.67g of m-diethynylbenzene and 20gTHF mixed solution to the constant pressure funnel, slowly add dropwise, and continue to heat to 63℃ and reflux for 2h. After cooling to room temperature, add 0.04mol of dimethyldichlorosilane monomer and 20gTHF, and heat to 63℃ and reflux for 1.5h again after the addition is completed.

[0094] Add 50g of 5% dilute hydrochloric acid to the solution obtained in the previous step, stir at room temperature for 30min, take out, filter, wash, separate, dry, filter twice, and rotary evaporate to finally obtain poly(m-diethynylbenzene-dimethylsilane) resin

[0095] The resin was cured in a muffle furnace by step-heating at 150°C / 2h+200°C / 2h+250°C / 2h+300°C / 2h+350°C / 2h.

[0096] The cured product in the embodiment was subjected to TGA test at a heating rate of 10°C / min in a nitrogen atmosphere and an air atmosphere, respectively, and the thermal decomposition temperature (Td5) at which the mass loss was 5% and the mass retention rate at 1000°C were respectively shown in the following table:

[0097]

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

[0099] All documents mentioned in the present invention are cited as references in this application, just as each document is cited as reference individually. In addition, it should be understood that after reading the above teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. A carborane-terminated borosilicate resin, characterized in that: The carborane-terminated borosilicate 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 to 50.

2. A method for preparing the carborane-terminated borosilicate resin according to claim 1, characterized in that: The steps include: (1) Under the protection of inert gas, at 25°C ± 5°C, magnesium, iodine and an organic solvent are mixed, ethyl bromide is added, and the mixture is reacted at 55-70°C for 1.5 hours to 3.5 hours to obtain an ethyl bromide Grignard reagent; magnesium, iodine and an organic solvent are mixed, 1-bromomethyl-o-carborane is added, and the mixture is reacted at 55-70°C for 1.5 hours to 3.5 hours to obtain a 1-bromomethyl-o-carborane Grignard reagent; (2) adding m-diethynylbenzene dropwise to the bromoethane Grignard reagent obtained in step (1), and reacting at 55-70° C. for 2-4 hours to obtain m-diethynylbenzene Grignard reagent; (3) Add the 1-bromomethyl-o-carborane Grignard reagent obtained in step (1) dropwise into the m-diethynylbenzene Grignard reagent obtained in step (2); then add dichlorosilane dropwise, and react at 55-70° C. for 1.5-3.5 hours to obtain the carborane-terminated borosilicate resin.

3. The preparation method according to claim 2, characterized in that: The method further comprises a post-processing step: After the reaction is completed, a dilute hydrochloric acid solution is added to the reaction solution, and after separation, the organic layer is concentrated to obtain a carborane-terminated borosilicate resin.

4. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of ethyl bromide to magnesium is 1:(1-1.5), preferably 1:1.1; and / or The molar ratio of 1-bromomethyl-o-carborane to magnesium is 1:(1-1.5), preferably 1:1.

25.

5. The preparation method according to claim 2, characterized in that: In step (1), the reaction time is 1.5 h to 2 h.

6. The preparation method according to claim 2, characterized in that: In step (2), the reaction time is 1.5 h to 2.5 h.

7. The preparation method according to claim 2, characterized in that: In step (3), the reaction time is 1.5 h to 2.5 h.

8. The preparation method according to claim 2, characterized in that: The molar ratio of dichlorosilane, 1-bromomethyl-o-carborane and m-diethynylbenzene is 1:(0.1-0.8):(1-0.7), preferably 1:(0.3-0.5):(0.9-0.8).

9. The preparation method according to claim 2, characterized in that: Step (3) comprises the following steps: dripping the 1-bromomethyl o-carborane Grignard reagent obtained in step (1) into the m-diethynylbenzene Grignard reagent obtained in step (2) by using air pressure through a flow guide device; dripping dichlorosilane for a dripping time of 0.5 to 1 hour, controlling the temperature during the dripping process at 30 to 40° C., and then reacting at 55 to 70° C. for 1.5 to 3.5 hours to obtain the carborane-terminated borosilicate resin, and cooling to room temperature after the reaction.

10. A carborane-terminated borosilicate resin polymer, characterized in that: The solidified material is obtained by solidifying carborane-terminated borosilicate resin.

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