Novel high-temperature-resistant carborane-siloxane resin as well as synthesis method and application thereof

Abstract

The invention discloses novel high-temperature-resistant carborane-siloxane resin as well as a synthesis method and application thereof. The carborane-siloxane resin disclosed by the invention is obtained by reacting a carborane monomer derivative with an organosilane monomer under the condition of a catalyst. The viscosity of the carborane-siloxane resin ranges from 300 mpa.s to 5000 mpa.s, the carborane-siloxane resin has the high-temperature performance higher than 800 DEG C, the residual weight can reach 90% or above at the temperature of 800 DEG C, and the carborane-siloxane resin has good ablation resistance; meanwhile, the composite material has good tolerance to neutron and gamma ray radiation, and can be used in the fields of aviation, aerospace, ships, nuclear power and the like.

Description

Technical Field

[0001] The invention relates to the preparation of a high temperature resistant material, and in particular to a novel high temperature resistant carborane-siloxane resin and a synthesis method and application thereof. Background Art

[0002] When an aircraft flies at high speed in the atmosphere, the aerodynamic friction causes the surface temperature of the aircraft to rise sharply. In order to prevent the aircraft from being burned, effective thermal protection measures must be taken to ensure the integrity of the structure. Thermal protection ablative coating is a sacrificial material that protects the aircraft from being burned. It has the advantages of high thermal protection efficiency and simple construction, and has become an effective method to solve the heat protection of various aircraft.

[0003] When examining ablation-resistant coatings, their quality is generally measured in terms of ablation performance, mechanical properties, and processing performance; heat-resistant coatings are composed of three parts: resin matrix system, filler system, and curing process. Among these three systems, if only relying on fillers to improve the performance of thermal protective coatings will often affect their process performance. For example, increased viscosity is not conducive to construction. The resin matrix, as a carrier for carrying fillers, needs to withstand higher temperature levels in order to coat more fillers at the corresponding temperature to meet the protection requirements of the thermal protective coating. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] A carborane-siloxane resin is obtained by reacting a carborane monomer derivative and an organic silane monomer under a catalyst condition.

[0006] According to an embodiment of the present invention, the structural formula of the carborane monomer derivative is shown in formula (A):

[0007]

[0008] In formula (A), M is selected from the residue of carborane, for example, -CB 10 H 10 C-; m is selected from 0 to 1000, for example, 1, 10, 100;

[0009] R 1 , R 2 , R 3 , R 4 , R 5 are the same or different and are independently selected from H, unsubstituted or optionally substituted with one, two or more R a Substituted C 1-20 Alkyl, C 2-20 Alkenyl, C 3-20 At least one of a cycloalkyl group and an aryl group; preferably, the R1 , R 2 , independently selected from H, unsubstituted or optionally substituted with one, two or more R a Substituted C 1-10 Alkyl, C 2-10 Alkenyl, C 3-10 Cycloalkyl and C 6-20 at least one of aromatic groups;

[0010] Every R a are the same or different and are independently selected from halogen, -CN, C 1-20 Alkyl, C 2-20 Alkenyl, C 1-20 Alkoxy and C 3-20 At least one of cycloalkyl; preferably, R a Can be selected from halogen, -CN, C 1-10 Alkyl, C 2-10 Alkenyl and C 3-10 At least one of cycloalkyl; exemplarily, R a Can be selected from F, Cl, Br, -CN, -CH 3 , -C 2 H 5 and -CH=CH 2 At least one of;

[0011] For example, R 1 , R 2 , R 3 , R 4 , R 5 The groups may be independently selected from at least one of methyl, ethyl, vinyl, phenyl, tolyl, and naphthyl.

[0012] Preferably, in formula (A), M is selected from the group consisting of an ortho-carborane residue, a meta-carborane residue, and a para-carborane residue.

[0013] Exemplarily, the structural formula of the meta-carborane residue is The * is the connection point.

[0014] Exemplarily, the structural formula of the residue of ortho-carborane is The * is the connection point.

[0015] Exemplarily, the structural formula of the residue of the para-carborane is The * is the connection point.

[0016] According to an embodiment of the present invention, the carborane monomer derivative is, for example, at least one selected from the compounds having formulae (A-1) to (A-3):

[0017]

[0018] Herein, m is selected from 0 to 1000, for example, 1, 10, or 100.

[0019] According to an embodiment of the present invention, the organic silane monomer is selected from one or more siloxanes such as 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane, etc.

[0020] According to an embodiment of the present invention, the molar ratio of the carborane monomer derivative to the organosilane monomer is 1:(0.2-2.5), for example, 1:0.5, 1:1, 1:1.5, 1:2.

[0021] According to an exemplary embodiment of the present invention, the structure of the carborane-siloxane resin is selected from at least one of the following formulas (I-1) to (I-5):

[0022]

[0023]

[0024] In formula (I-1) to formula (I-5), n is selected from 1 to 10000, for example, 10, 100, 1000; m is selected from 0 to 1000, for example, 1, 10, 100.

[0025] According to an embodiment of the present invention, the carborane-siloxane resin has a high temperature performance exceeding 800°C.

[0026] According to an embodiment of the present invention, the carborane-siloxane resin has good resistance to neutron and gamma ray radiation.

[0027] According to an embodiment of the present invention, the viscosity of the carborane-siloxane resin is 300 mPa.s-5000 mPa.s, for example, 500 mPa.s, 1000 mPa.s, 2000 mPa.s, 3000 mPa.s, 4000 mPa.s, or 5000 mPa.s.

[0028] The present invention also provides a method for synthesizing the above-mentioned carborane-siloxane resin, which comprises the following steps:

[0029] A. preparing carborane monomer derivatives;

[0030] B. preparing organosilane monomer;

[0031] C. Synthesis of carborane carborane-siloxane resin: The carborane monomer derivative of step A is mixed with the organosilicon silane monomer of step B, a catalyst is added, and the mixture is reacted under an inert atmosphere to obtain the carborane-siloxane resin.

[0032] According to an embodiment of the present invention, in step A, the preparation method of the carborane monomer derivative can be selected by a method known in the art, as long as the carborane monomer derivative can be obtained, and the carborane monomer derivative has the meaning as described above.

[0033] According to an exemplary embodiment of the present invention, the preparation method of the carborane monomer derivative is as follows:

[0034] (1) subjecting a carborane monomer to lithiation with butyl lithium to obtain a first intermediate;

[0035] (2) reacting the first intermediate with chlorosilane under certain conditions to obtain a second intermediate;

[0036] (3) The second monomer is reacted with an appropriate amount of water to obtain a carborane monomer derivative through a hydrolysis reaction.

[0037] Preferably, the carborane monomer is selected from ortho-carborane, meta-carborane and para-carborane.

[0038] Exemplarily, the ortho-carborane is

[0039] Exemplarily, the meta-carborane is

[0040] Exemplarily, the para-carborane is

[0041] Preferably, the first intermediate is selected from at least one of the following structures:

[0042]

[0043] Preferably, the second intermediate is selected from at least one of the following structures:

[0044]

[0045] Preferably, in the method for preparing the carborane monomer derivative, in step (1), the reaction temperature is -10 to 50° C., and the reaction time is 30 min to 5 h.

[0046] Preferably, in the method for preparing the carborane monomer derivative, a reaction solvent may be added in steps (1) to (3), and the reaction solvent is one or a mixed solution of n-hexane, ethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, tetrahydropyran, toluene, n-heptane, etc.

[0047] Preferably, in step (2), the reaction temperature is -10 to 80°C, and the reaction time is 30 min to 5 h.

[0048] Preferably, in step (3), the temperature of the hydrolysis reaction is -10 to 60°C, and the time of the hydrolysis reaction is 20 min to 5 h.

[0049] According to an embodiment of the present invention, in step B, the organosilane monomer has the meaning as described above, for example, one or more selected from 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane and the like silanes.

[0050] According to an embodiment of the present invention, in step C, the catalyst is selected from one or more of chloroplatinic acid, a Pt catalyst coordinated with isopropanol, tri(pentafluorophenyl)borane, and boron trifluoride. Exemplarily, the Pt catalyst can be selected from catalysts known in the art, such as a Karstedt catalyst.

[0051] According to an embodiment of the present invention, in step C, the solvent is one or more of toluene, xylene, heptane, dioxane, tetrahydrofuran, tetrahydropyran, n-hexane, petroleum ether, diethylene glycol dimethyl ether, and ethylene glycol dimethyl ether.

[0052] According to an embodiment of the present invention, in step C, the molar ratio of the carborane monomer derivative to the organosilicon silane monomer is 1:(0.2-2.5), for example, 1:0.5, 1:1, 1:1.5, 1:2.

[0053] According to an embodiment of the present invention, in step C, the mass fraction of the catalyst is 0.1% to 8%.

[0054] According to an embodiment of the present invention, in step C, a solvent may be further added.

[0055] According to an embodiment of the present invention, in step C, the mass fraction of the solvent is 50% to 200%.

[0056] According to an embodiment of the present invention, in step C, the reaction conditions are: the reaction temperature is -20°C to 150°C, and the reaction time is 30min to 24h.

[0057] According to an embodiment of the present invention, the synthesis method further comprises: D. After the reaction of step C is completed, adding an organic solvent to the reaction system for extraction, standing and stratifying, removing the solvent layer, and then adding water to wash and neutralize;

[0058] According to an embodiment of the present invention, the synthesis method further comprises: E. high temperature vacuum drying: vacuum rotary evaporation of the product obtained in step D, high temperature vacuum treatment, and cooling to room temperature.

[0059] According to an embodiment of the present invention, in step D, the organic extractant is one or more of ethanol, methanol, toluene, diethanol, tetrahydrofuran, n-hexane, petroleum ether, etc.

[0060] According to an embodiment of the present invention, in step E, the vacuum rotary evaporation conditions can be selected from conditions known in the art, such as 40-100° C. and 0.5-2 h to remove the solvent.

[0061] According to an embodiment of the present invention, in step E, the high temperature vacuum conditions can be selected by methods known in the art, such as 110-160° C. and 1-24 h.

[0062] The present invention also provides the application of the carborane-siloxane resin, which can be used in the fields of aviation, aerospace, shipbuilding and nuclear power.

[0063] Beneficial Effects

[0064] The novel high-temperature resistant carborane-siloxane resin prepared by the present invention has a viscosity between 300 MPa.s and 5000 MPa.s. The carborane-siloxane resin of the present invention has a high-temperature performance exceeding 800°C, and the residual weight at 800°C is above 85% and can even reach above 90%, and has good ablation resistance; at the same time, it has good tolerance to neutron and gamma-ray radiation, and can be used in the fields of aviation, aerospace, shipbuilding, nuclear power, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 Schematic diagram of the reaction route of hydroxycarborane;

[0066] Figure 2 Schematic diagram of the preparation route of carborane monomer derivatives;

[0067] Figure 3 Schematic diagram of the reaction route of carborane-siloxane resin.

[0068] Figure 4 The reaction monomers and products of Example 1 29 Si NMR (A), the reaction monomer and product of Example 7 29 Si NMR (B). DETAILED DESCRIPTION

[0069] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0070] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0071] The test method of residual weight (thermal weight loss) in the following examples is: in an air atmosphere, the gas flow rate is 80 mL / min, heating starts from 50° C. and is heated to 800° C. at a heating rate of 10° C. / min.

[0072] Reference example

[0073] Tetramethyldisiloxane (MM H ) and tetramethyltetravinylsiloxane in a molar ratio of 1:1, and polymerized in the presence of a Pt catalyst (Karstedt catalyst, commercially available) to obtain a cross-linked resin. The residual weight was tested in an air atmosphere, and the residual weight of the cross-linked resin was 5%.

[0074] Example 1

[0075] The preparation method of carborane-siloxane resin is as follows:

[0076] A: The preparation method of the meta-carborane monomer derivative specifically includes:

[0077] (1) Under nitrogen protection, 11 ml of butyl lithium (2.4 mol / L) was placed in a 150 mL round-bottom flask, diluted with 50 mL of tetrahydrofuran, and 20 mL of a tetrahydrofuran solution of meta-carborane (1.44 g) was added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 3 h to obtain a first intermediate lithiated carborane;

[0078] (2) Then, dimethyldichlorosilane was added, and the molar ratio of meta-carborane to dimethyldichlorosilane was 1:2; the reaction was carried out at room temperature for 15 hours, and then 5 ml of deionized water was added, and the reaction was hydrolyzed at 0° C. for 30 minutes to obtain the second intermediate hydroxycarborane. The reaction route is as follows: Figure 1 As shown; extraction, concentration of the organic phase and recrystallization can obtain 2.1 g of the second intermediate hydroxycarborane;

[0079] (3) Then, 1.0 g of hydroxycarborane, 0.92 g of tetramethyldisiloxane, 0.3% of trifluoromethanesulfonic acid, and 30 ml of toluene were reacted at 80° C. for 15 h to obtain 2 g of the target product 1,7-bis(hydrogentetramethyldisiloxanesilyl)-carborane (HCB-2), which was recorded as a meta-carborane monomer derivative.

[0080] B: Prepare the organosilane monomer: select tetramethyltetravinylcyclotetrasiloxane;

[0081] C: Synthesis of silicone resin:

[0082] 1 g of the meta-carborane monomer derivative in step A and 1.2 g of the organosilane monomer in step B were mixed in a 25 ml single-necked bottle, and 0.5% Pt catalyst (Karstedt catalyst, commercially available) and 5 ml of toluene solvent were added. The mixture was heated at 60 ° C and N 2 The mixture was stirred and reacted for 5 h under a nitrogen atmosphere to obtain a crude carborane-siloxane resin.

[0083] D: Extraction and washing of products:

[0084] The crude carborane-siloxane resin obtained in step C was washed three times with toluene and ethanol.

[0085] E: High temperature vacuum drying:

[0086] The product after washing in step D was subjected to rotary evaporation at 60° C. for 1 h to remove the solvent, and then placed in a vacuum oven at 80° C. for 4 h and cooled to obtain a carborane-siloxane resin with a viscosity of 1500 mPa.s.

[0087] The carborane-siloxane resin obtained in step E is subjected to TGA to obtain an ablation-resistant resin matrix with a residual weight of 88.54% at 800°C.

[0088] Example 2

[0089] The preparation method of carborane-siloxane resin is as follows:

[0090] A: The preparation method of the ortho-carborane monomer derivative specifically includes:

[0091] (1) Under nitrogen protection, 11 ml of butyl lithium (2.4 mol / L) was placed in a 150 mL round-bottom flask, diluted with 50 mL of tetrahydropyran, and 40 mL of a tetrahydropyran solution of ortho-carborane (1.44 g) was added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 3 h to obtain a first intermediate lithiated carborane;

[0092] (2) Then, dimethyldichlorosilane was added, and the molar ratio of ortho-carborane to dimethyldichlorosilane was 1:2; the reaction was carried out at room temperature for 15 hours, and then 5 ml of deionized water was added and hydrolyzed at 0°C for 30 minutes to obtain the second intermediate hydroxycarborane. The reaction scheme is as follows: Figure 1 As shown; extraction, concentration of the organic phase and recrystallization can give 3.2 g of the second intermediate hydroxycarbon borane.

[0093] (3) Then, 1.0 g of hydroxycarborane, 1.00 g of tetramethyldivinyldisiloxane, 0.4% of trifluoromethanesulfonic acid, and 30 ml of toluene were reacted at 80° C. for 20 h to obtain 1.62 g of 1,2-bis(vinyltetramethyldisiloxanesilyl)-carborane, which is an ortho-carborane monomer derivative.

[0094] B: Prepare the organosilane monomer: select tetramethylcyclotetrasiloxane;

[0095] C: Synthesis of silicone resin:

[0096] Take 1 g of the ortho-carborane monomer derivative in step A and 1.3 g of the organosilane monomer in step B in a 25 ml single-necked bottle, add 0.3% Pt catalyst (Karstedt catalyst, commercially available) and 5 ml of toluene solvent, and heat at 80°C, N 2 The target product, a crude carborane-siloxane resin, was obtained by stirring the reaction for 5 h under a nitrogen atmosphere.

[0097] D: Extraction and washing of products:

[0098] The crude carborane-siloxane resin obtained in step C was washed three times with toluene and ethanol.

[0099] E: High temperature vacuum drying:

[0100] The product obtained in step D was subjected to rotary evaporation at 60° C. for 1 h to remove the solvent, and then placed in a vacuum oven at 80° C. for 4 h and cooled to obtain a carborane-siloxane resin with a viscosity of 2500 mPa.s.

[0101] The carborane-siloxane resin obtained in step E is subjected to TGA to obtain an ablation-resistant resin matrix with a residual weight of 85.60% at 800°C.

[0102] Example 3

[0103] The preparation method of carborane-siloxane resin is as follows:

[0104] A: The preparation method of the para-carborane monomer derivative specifically includes:

[0105] (1) Under nitrogen protection, 11 ml of butyl lithium (2.4 mol / L) was placed in a 150 mL round-bottom flask, diluted with 60 mL of diethanol diethyl ether, and 20 mL of a diethanol diethyl ether solution of para-carborane (1.44 g) was added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 6 h to obtain a first intermediate lithiated carborane;

[0106] (2) Then, dimethyldichlorosilane was added, and the molar ratio of para-carborane to dimethyldichlorosilane was 1:2; the reaction was carried out at room temperature for 10 hours, and then 5 ml of deionized water was added and hydrolyzed at 0°C for 30 minutes to obtain the second intermediate hydroxycarborane. The reaction route is as follows: Figure 1 As shown; extraction, concentration of the organic phase and recrystallization to obtain the second intermediate hydroxycarborane 2.8g;

[0107] (3) Then, 1.0 g of hydroxycarborane, 0.96 g of tetramethyldisiloxane, 0.35% of trifluoromethanesulfonic acid, and 30 ml of toluene were reacted at 80° C. for 15 h to obtain 1.71 g of 1,12-bis(hydrogentetramethyldisiloxanesilyl)-carborane, which is a para-carborane monomer derivative.

[0108] B: Prepare the organosilane monomer: select tetramethyltetravinylcyclotetrasiloxane;

[0109] C: Synthesis of silicone resin:

[0110] 1 g of the para-carborane monomer derivative in step A and 1.25 g of the organosilane monomer in step B were respectively placed in a 25 ml single-necked bottle, 0.6% Pt catalyst (Karstedt catalyst, commercially available) and 5 ml of toluene solvent were added, and the mixture was heated at 60°C and N 2 The mixture was stirred and reacted for 3 h under a nitrogen atmosphere to obtain a crude carborane-siloxane resin.

[0111] D: Extraction and washing of products:

[0112] The crude carborane-siloxane resin obtained in step C was washed three times with toluene and ethanol.

[0113] E: High temperature vacuum drying:

[0114] The crude carborane-siloxane resin obtained in step D was subjected to rotary evaporation at 70° C. for 1 h to remove the solvent, and then placed in a vacuum oven at 80° C. for 4 h and cooled to obtain a carborane-siloxane resin with a viscosity of 5000 mPa.s.

[0115] The carborane-siloxane resin obtained in step E is subjected to TGA to obtain an ablation-resistant resin matrix with a residual weight of 90.04% at 800°C.

[0116] Example 4

[0117] The preparation method of carborane-siloxane resin is as follows:

[0118] A: The preparation method of the meta-carborane monomer derivative specifically includes:

[0119] (1) Under nitrogen protection, 11 ml of butyl lithium (2.4 mol / L) was placed in a 150 mL round-bottom flask, diluted with 50 mL of tetrahydrofuran, and 20 mL of a tetrahydrofuran solution of meta-carborane (1.44 g) was added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 3 h to obtain a first intermediate lithiated carborane;

[0120] (2) Then, dimethyldichlorosilane was added, and the molar ratio of meta-carborane to dimethyldichlorosilane was 1:2; the reaction was carried out at room temperature for 7 hours, and then 5 ml of deionized water was added and hydrolyzed at 0° C. for 30 minutes to obtain the second intermediate hydroxycarborane. The reaction scheme is as follows: Figure 1 As shown; extraction, concentration of the organic phase and recrystallization to obtain the second intermediate hydroxycarborane 2.1g, yield 72%;

[0121] (3) Then, 1.0 g of hydroxycarborane, 0.96 g of tetramethyldisiloxane, 0.3% of trifluoromethanesulfonic acid, and 30 ml of toluene were reacted at 80° C. for 15 h to obtain 1.52 g of 1,7-bis(hydrogentetramethyldisiloxanesilyl)-carborane, which is a meta-carborane monomer derivative.

[0122] B: Prepare the organosilane monomer: select tetramethyltetravinylcyclotetrasiloxane;

[0123] C: Synthesis of silicone resin:

[0124] Take 1 g of the meta-carborane monomer derivative in step A and 1.2 g of the organosilane monomer in step B in a 25 ml single-necked bottle, add 0.2% Pt catalyst (Karstedt catalyst, purchased from outside) and 5 ml of toluene solvent, and heat at 60°C, N 2 The target product, a crude carborane-siloxane resin, was obtained by stirring the reaction for 5 h under a nitrogen atmosphere.

[0125] D: Extraction and washing of products:

[0126] The crude carborane-siloxane resin obtained in step C was washed three times with toluene and ethanol.

[0127] E: High temperature vacuum drying:

[0128] The product obtained in step D was subjected to rotary evaporation at 60° C. for 2 h to remove the solvent, and then placed in a vacuum oven at 80° C. for 8 h and cooled to obtain a carborane-siloxane resin with a viscosity of 4500 mPa.s.

[0129] The carborane-siloxane resin obtained in step E is subjected to TGA to obtain an ablation-resistant resin matrix with a residual weight of 84.04% at 800°C.

[0130] Example 5

[0131] The preparation method of carborane-siloxane resin is as follows:

[0132] A: The preparation method of the para-carborane monomer derivative specifically includes:

[0133] (1) Under nitrogen protection, 11 ml of butyl lithium (2.4 mol / L) was placed in a 150 mL round-bottom flask, diluted with 50 mL of tetrahydrofuran, and 20 mL of a tetrahydrofuran solution of para-carborane (1.44 g) was added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 3 h to obtain a first intermediate lithiated carborane;

[0134] (2) Then, dimethyldichlorosilane was added, and the molar ratio of para-carborane to dimethyldichlorosilane was 1:2; the reaction was carried out at room temperature for 6 hours, and then 5 ml of deionized water was added and hydrolyzed at 0° C. for 30 minutes to obtain the second intermediate hydroxycarborane. The reaction route is as follows: Figure 1 As shown; extraction, concentration of the organic phase and recrystallization can give 2.3 g of the second intermediate hydroxycarbon borane.

[0135] (3) Then, 1.0 g of hydroxycarborane, 1.06 g of tetramethyldisiloxane, 0.6% of trifluoromethanesulfonic acid, and 30 ml of toluene were reacted at 80° C. for 5 h to obtain 1.52 g of the target product 1,12-bis(hydrogen tetramethyldisiloxanesilyl)-carborane, which is a para-carborane monomer derivative.

[0136] B: Prepare the organosilane monomer: select tetramethyltetravinylcyclotetrasiloxane;

[0137] C: Synthesis of silicone resin:

[0138] 1 g of the para-carborane monomer derivative in step A and 1.2 g of the organosilane monomer in step B were respectively placed in a 25 ml single-necked bottle, 0.7% Pt catalyst (Karstedt catalyst, commercially available) and 5 ml of toluene solvent were added, and the mixture was heated at 60°C and N 2 The target product, a crude carborane-siloxane resin, was obtained by stirring the reaction for 3 h under a nitrogen atmosphere.

[0139] D: Extraction and washing of products:

[0140] The crude carborane-siloxane resin obtained in step C was washed three times with toluene and ethanol.

[0141] E: High temperature vacuum drying:

[0142] The product obtained in step D was subjected to rotary evaporation at 60° C. for 2 h to remove the solvent, and then placed in a vacuum oven at 60° C. for 8 h and cooled to obtain a carborane-siloxane resin with a viscosity of 3500 mPa.s.

[0143] The carborane-siloxane resin obtained in step E is subjected to TGA to obtain an ablation-resistant resin matrix with a residual weight of 87.14% at 800°C.

[0144] Example 6

[0145] The preparation method of carborane-siloxane resin is as follows:

[0146] A: The preparation method of the ortho-carborane monomer derivative specifically includes:

[0147] (1) Under nitrogen protection, 11 ml of butyl lithium (2.4 mol / L) was placed in a 150 mL round-bottom flask, diluted with 50 mL of tetrahydrofuran, and 20 mL of ether solution of ortho-carborane (2.88 g) was added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 3 h to obtain the first intermediate lithiated carborane;

[0148] (2) Then, dimethyldichlorosilane was added, and the molar ratio of ortho-carborane to dimethyldichlorosilane was 1:2; the reaction was carried out at room temperature for 2 hours, and then 5 ml of deionized water was added and hydrolyzed at 0° C. for 30 minutes to obtain the second intermediate hydroxycarborane. The reaction route is as follows: Figure 1 As shown; extraction, concentration of the organic phase and recrystallization to obtain the second intermediate hydroxycarborane 2.8g;

[0149] (3) Then, 1.0 g of hydroxycarborane, 1.40 g of tetramethyldivinyldisiloxane, 0.45% of trifluoromethanesulfonic acid, and 30 ml of toluene were reacted at 100° C. for 5 h to obtain 1.52 g of 1,2-bis(vinyltetramethyldisiloxanesilyl)-carborane, which is an ortho-carborane monomer derivative.

[0150] B: Prepare the organosilane monomer: select tetramethylcyclotetrasiloxane;

[0151] C: Synthesis of silicone resin:

[0152] Take 1 g of the ortho-carborane monomer derivative in step A and 1.2 g of the organosilane monomer in step B in a 25 ml single-necked bottle, add 0.55% Pt catalyst (Karstedt catalyst, commercially available) and 5 ml of toluene solvent, and heat at 70°C and N 2 The target product, a crude carborane-siloxane resin, was obtained by stirring the reaction for 3 h under a nitrogen atmosphere.

[0153] D: Extraction and washing of products:

[0154] The product obtained in step C was washed three times with toluene and ethanol.

[0155] E: High temperature vacuum drying:

[0156] The product obtained in step D was subjected to rotary evaporation at 60° C. for 1 h to remove the solvent, and then placed in a vacuum oven at 90° C. for 3 h and cooled to obtain a carborane-siloxane resin with a viscosity of 4800 mPa.s.

[0157] The carborane-siloxane resin obtained in step E is subjected to TGA to obtain an ablation-resistant resin matrix with a residual weight of 91.24% at 800°C.

[0158] Example 7

[0159] The preparation method of carborane-siloxane resin is as follows:

[0160] A: The preparation method of the meta-carborane monomer derivative specifically includes:

[0161] (1) Under nitrogen protection, 11 ml of butyl lithium (2.4 mol / L) was placed in a 150 mL round-bottom flask, diluted with 50 mL of tetrahydrofuran, and 20 mL of ether solution of meta-carborane (2.88 g) was added dropwise at room temperature. After the addition was complete, the reaction was continued at room temperature for 3 h to obtain the first intermediate lithiated carborane;

[0162] (2) Then, dimethyldichlorosilane was added, and the molar ratio of meta-carborane to dimethyldichlorosilane was 1:2; the reaction was carried out at room temperature for 2 hours, and then 5 ml of deionized water was added and hydrolyzed at 0° C. for 30 minutes to obtain the second intermediate hydroxycarborane. The reaction route is as follows: Figure 1 As shown; extraction, concentration of the organic phase and recrystallization to obtain the second intermediate hydroxycarborane 2.8g;

[0163] (3) Then, 1.0 g of hydroxycarborane, 1.40 g of tetramethyldivinylsiloxane, 0.35% of trifluoromethanesulfonic acid, and 30 ml of toluene were reacted at 100° C. for 5 h to obtain 1.52 g of 1,2-bis(vinyltetramethyldisiloxanesilyl)-carborane, which is a meta-carborane monomer derivative.

[0164] B: Prepare the organosilane monomer: select tetramethylcyclotetrasiloxane;

[0165] C: Synthesis of silicone resin:

[0166] Take 1 g of the meta-carborane monomer derivative in step A and 1.2 g of the organosilane monomer in step B in a 25 ml single-necked bottle, add 0.55% Pt catalyst (Karstedt catalyst, commercially available) and 5 ml of toluene solvent, and heat at 70°C, N 2 The target product, a crude carborane-siloxane resin, was obtained by stirring the reaction for 3 h under a nitrogen atmosphere.

[0167] D: Extraction and washing of products:

[0168] The product obtained in step C was washed three times with toluene and ethanol.

[0169] E: High temperature vacuum drying:

[0170] The product obtained in step D was subjected to rotary evaporation at 60° C. for 1 h to remove the solvent, and then placed in a vacuum oven at 90° C. for 3 h and cooled to obtain a carborane-siloxane resin with a viscosity of 3800 mPa.s.

[0171] The carborane-siloxane resin obtained in step E is subjected to TGA to obtain an ablation-resistant resin matrix with a residual weight of 92.24% at 800°C.

[0172] The above is a description of the exemplary embodiments of the present invention. However, the protection scope of the present application is not limited to the above embodiments. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A carborane-siloxane resin, characterized in that: The carborane-siloxane resin is obtained by reacting a carborane monomer derivative and an organic silane monomer under a catalyst condition.

2. The carborane-siloxane resin according to claim 1, characterized in that The structural formula of the carborane monomer derivative is shown in formula (A): In formula (A), M is selected from the residue of carborane; m is selected from 0 to 1000; R1, R2, R3, R4, R5 are the same or different and are independently selected from H, unsubstituted or optionally substituted with one, two or more R a Substituted C 1-20 Alkyl, C 2-20 Alkenyl, C 3-20 at least one of a cycloalkyl group and an aryl group; Every R a are the same or different and are independently selected from halogen, -CN, C 1-20 Alkyl, C 2-20 Alkenyl, C 1-20 Alkoxy and C 3-20 At least one of cycloalkyl groups. Preferably, in formula (A), M is selected from the group consisting of an ortho-carborane residue, a meta-carborane residue, and a para-carborane residue. Preferably, said R1, R2, are independently selected from H, unsubstituted or optionally substituted with one, two or more R a Substituted C 1-10 Alkyl, C 2-10 Alkenyl, C 3-10 Cycloalkyl and C 6-20 At least one of the aromatic groups. Preferably, R a Selected from halogen, -CN, C 1-10 Alkyl, C 2-10 Alkenyl and C 3-10 At least one of cycloalkyl; exemplarily, R a At least one selected from F, Cl, Br, -CN, -CH3, -C2H5 and -CH=CH2.

3. The carborane-siloxane resin according to claim 1 or 2, characterized in that: The carborane monomer derivative is selected from at least one of the compounds having formula (A-1) to (A-3): Here, m is selected from 0 to 1000.

4. The carborane-siloxane resin according to any one of claims 1 to 3, characterized in that The organosilane monomer is selected from one or more siloxanes such as 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, and 3,5-bis(dimethylsiloxy)-1,1,7,7-tetramethyl-3,5-diphenyltetrasiloxane. Preferably, the molar ratio of the carborane monomer derivative to the organosilane monomer is 1:(0.2-2.5).

5. The carborane-siloxane resin according to any one of claims 1 to 4, characterized in that The carborane-siloxane resin has high temperature performance exceeding 800°C. Preferably, the carborane-siloxane resin has good resistance to neutron and gamma ray radiation. Preferably, the viscosity of the carborane-siloxane resin is 300 mPa.s-5000 mPa.s.

6. The method for synthesizing the carborane-siloxane resin according to any one of claims 1 to 5, characterized in that: The synthesis method comprises the following steps: A. preparing carborane monomer derivatives; B. preparing organosilane monomer; C. Synthesis of carborane carborane-siloxane resin: The carborane monomer derivative of step A is mixed with the organosilicon silane monomer of step B, a catalyst is added, and the mixture is reacted under an inert atmosphere to obtain the carborane-siloxane resin.

7. The synthesis method according to claim 6, characterized in that The preparation method of the carborane monomer derivative is as follows: (1) subjecting a carborane monomer to lithiation with butyl lithium to obtain a first intermediate; (2) reacting the first intermediate with chlorosilane under certain conditions to obtain a second intermediate; (3) The second monomer is reacted with an appropriate amount of water to obtain a carborane monomer derivative through a hydrolysis reaction.

8. The synthesis method according to claim 6 or 7, characterized in that: The carborane monomer is selected from ortho-carborane, meta-carborane and para-carborane. Preferably, the first intermediate is selected from at least one of the following structures: Preferably, the second intermediate is selected from at least one of the following structures: Preferably, in the method for preparing the carborane monomer derivative, in step (1), the reaction temperature is -10 to 50° C., and the reaction time is 30 min to 5 h. Preferably, in the method for preparing the carborane monomer derivative, in steps (1)-(3), a reaction solvent is also added, and the reaction solvent is one or a mixed solution of n-hexane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, tetrahydropyran, toluene, n-heptane, etc. Preferably, in step (2), the reaction temperature is -10 to 80°C, and the reaction time is 30 min to 5 h. Preferably, in step (3), the temperature of the hydrolysis reaction is -10 to 60°C, and the time of the hydrolysis reaction is 20 min to 5 h.

9. The synthesis method according to any one of claims 6 to 8, characterized in that: In step C, the catalyst is selected from one or more of chloroplatinic acid, a Pt catalyst coordinated with isopropanol, tri(pentafluorophenyl)borane, and boron trifluoride. Preferably, in step C, the solvent is one or more of toluene, xylene, heptane, dioxane, tetrahydrofuran, tetrahydropyran, n-hexane, petroleum ether, diethylene glycol dimethyl ether, and ethylene glycol dimethyl ether. Preferably, in step C, the molar ratio of the carborane monomer derivative to the organosilicon silane monomer is 1:(0.2-2.5). Preferably, in step C, the mass fraction of the catalyst is 0.1% to 8%. Preferably, in step C, the reaction conditions are: reaction temperature is -20°C to 150°C, and reaction time is 30 min to 24 h.

10. Use of the carborane-siloxane resin according to any one of claims 1 to 5 in the fields of aviation, aerospace, shipbuilding and nuclear power.

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