CN110725133A - Heat-resistant textile based on carborane ceramic coating - Google Patents
Heat-resistant textile based on carborane ceramic coating Download PDFInfo
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- CN110725133A CN110725133A CN201911097296.2A CN201911097296A CN110725133A CN 110725133 A CN110725133 A CN 110725133A CN 201911097296 A CN201911097296 A CN 201911097296A CN 110725133 A CN110725133 A CN 110725133A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/56—Boron-containing linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
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Abstract
The invention discloses a carborane ceramic coating-based heat-resistant textile, which comprises an aramid fiber textile and a carborane ceramic coating; the carborane ceramic is prepared from a carborane ceramic precursor; the precursor is supported by using a cyclic silazane as a framework, has a cross-linked net structure, and has good ceramic yield during further cross-linking, so that a compact ceramic coating can be formed on the surface of the aramid fiber. The provided precursor has simple preparation process, mild preparation reaction conditions and easily obtained raw materials, and is suitable for industrial amplification production. The aramid fiber textile treated by the coating has excellent heat resistance and oxidation resistance.
Description
The invention belongs to a carborane ceramic coating-based heat-resistant textile and a preparation method thereof, and belongs to divisional application of invention application with application date of 2017, 5 and 8 and application number of 2017103190069, which belongs to the technical part of products.
Technical Field
The invention relates to a carborane ceramic coating-based heat-resistant textile and a preparation method thereof, belonging to the field of preparation and application of high-temperature-resistant polymers and composite materials.
Background
The high temperature resistant textile has wide application in the aspects of high temperature filtration and protective clothing. The SiBCN ceramic serving as a novel high-performance ceramic material has the advantages of strong high-temperature resistance, high oxidation resistance, good high-temperature creep resistance, high hardness, wear resistance, small linear expansion coefficient, chemical corrosion resistance and the like. The SiBCN coating is used as an interface material between the fiber and the ceramic matrix, so that the wettability of the fiber and the ceramic matrix can be improved; in the preparation method of the SiBCN quaternary ceramic material, the simplest method is that the cyclic silazane is borated, and the ceramic body is obtained by utilizing the reactive crosslinking of the cyclic silazane, wherein, methyl vinyl dichlorosilane is used as a raw material, a series of boron-based cyclic silazane is synthesized through hydroboration, ammonolysis and thermal polymerization, and the boron-based cyclic silazane is converted into the Si-B-C-N quaternary system ceramic which has better high-temperature stability than the Si-C-N ternary system ceramic. However, when the precursor compound is prepared by this method, the intermediate organoborane is extremely toxic and has poor operability, and it is difficult to industrially produce the precursor compound.
Disclosure of Invention
The invention aims to disclose a carborane ceramic coating-based heat-resistant textile and a preparation method thereof, which have good heat resistance, good flexibility and are beneficial to bonding.
A preparation method of a carborane ceramic coating-based heat-resistant textile comprises the following steps:
(1) 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane is used as a raw material and reacts under an alkaline condition and a metal catalyst to prepare the 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane;
(2) the 1,3, 5-trimethyl-1, 3, 5-tri- (tert-butyl-phenyl) -trisilazane is prepared from dimethylchlorosilane and trivinyl trimethyl cyclotrisilazane by reaction under the action of metal catalystβ- (dimethylchlorosilyl) ethyl]A cyclotrisilazane;
(3) 1,1 ' -hydrocarbon silicon methylene-2, 2 ' -bis (dimethyl hydroxyl silicon base) dicarboborane, 1,3, 5-trimethyl-1, 3, 5-tri [ alpha ], [ beta ] -methyl-2, 2 ' -bis (dimethyl hydroxyl silicon base)β- (dimethylchlorosilyl) ethyl]Preparing a carborane ceramic precursor by using cyclotrisilazane as a raw material in the presence of triethylamine;
(4) preparing a carborane ceramic precursor system by taking a carborane ceramic precursor, a solvent, a silane coupling agent and an epoxide as raw materials;
(5) soaking the textile in a carborane ceramic precursor system; the drying treatment results in a heat resistant textile based on a carborane ceramic coating.
In the technical proposal, the device comprises a base,
mixing sodium hydroxide with water, adding sodium dihydrogen phosphate monohydrate, mixing to prepare a buffer solution, and adding an ether solvent and a metal catalyst; then adding aromatic hydrocarbon solution of 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethyl silicon base) dicarboborane to react to prepare 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane;
adding a metal catalyst into a trivinyl trimethyl cyclotrisilazane arene solution in an inert atmosphere; then adding a dimethyl chlorosilane aromatic hydrocarbon solution; reaction to prepare 1,3, 5-trimethyl-1, 3, 5-tris [ alpha ], [ beta ] -aβ- (dimethylchlorosilyl) ethyl]A cyclotrisilazane;
the step (3) is to add 1,1 ' -hydrocarbyl silylmethylene-2, 2 ' -bis (dimethylhydroxysilyl) dicarboborane aromatic hydrocarbon solution containing triethylamine dropwise into the 1,3, 5-trimethyl-1, 3, 5-tris [ alpha ], [ beta ] -methyl-2, 2 ' -bis (dimethylhydroxysilyl) dicarboborane aromatic hydrocarbon solutionβ- (dimethylchlorosilyl) ethyl]Preparation of carborane ceramic precursor by reaction in cyclotrisilazane；
Dissolving a carborane ceramic precursor in a halogenated alkane solvent, and then adding an epoxy silane coupling agent and a diisopropadiene diepoxide to prepare a carborane ceramic precursor system;
and (5) soaking the textile in the carborane ceramic precursor system for 0.5 ~ 1 hours, and air-drying at room temperature to obtain the carborane ceramic coating-based heat-resistant textile.
In the above technical solution, the 1,1 '-hydrocarbylsilylene-2, 2' -bis (dimethylsilyl) dicarboborane is 1,1 '-methylphenylsilylene-2, 2' -bis (dimethylsilyl) dicarboborane or 1,1 '-diphenylsilylene-2, 2' -bis (dimethylsilyl) dicarboborane; the metal catalyst is a palladium carbon catalyst or a platinum carbon catalyst; the ether solvent is 1, 4-dioxane, and the aromatic hydrocarbon is toluene and/or xylene; the inert atmosphere is nitrogen atmosphere; the halogenated alkane solvent is one or more of dichloromethane, dichloroethane and trichloromethane; the textile is aramid fiber textile.
In the technical proposal, the device comprises a base,
in the step (1), the mass ratio of sodium hydroxide, water, sodium dihydrogen phosphate monohydrate, a metal catalyst and 1,1 '-hydrocarbyl silyl methylene-2, 2' -bis (dimethyl silicon base) dicarboborane is (0.2 ~ 2): (20 ~ 200): (0.2 ~ 5): (0.1 ~ 2): 0.5 ~ 5), the reaction temperature is 25 ℃ ~ 65 ℃, and the reaction time is 1 ~ 48 hours;
in the step (2), the mass ratio of the trivinyl trimethyl cyclotrisilazane to the metal catalyst to the dimethylchlorosilane is (0.5 ~ 5) to (0.001 ~ 0.2.2) to (0.5 ~ 5), the reaction temperature is 25 ℃ and ~ 85 ℃ and the reaction time is 1 ~ 48 hours;
in the step (3), the mass ratio of triethylamine to 1,1 '-alkyl silyl methylene-2, 2' -bis (dimethyl hydroxyl silyl) dicarboborane is (0.5 ~ 10) to (1 ~ 5), the reaction temperature is 25 ℃, the reaction time is ~ 75 ℃, and the reaction time is 1 ~ 48 hours;
in the step (4), the mass concentration of the carborane ceramic precursor system is 1% ~ 40%, and the mass ratio of the carborane ceramic precursor, the epoxy silane coupling agent and the diisopropadiene diepoxide is 1: 0.05: 0.1.
In the technical scheme, the carborane ceramic coating-based heat-resistant textile obtained in the step (5) is repeatedly subjected to the step (4) and the step (5), so that the carborane ceramic coating-based heat-resistant textile is obtained.
The invention also discloses a carborane ceramic coating-based heat-resistant textile, which comprises an aramid textile and a carborane ceramic coating; the carborane ceramic is prepared from a carborane ceramic precursor; the chemical structural formula of the carborane ceramic precursor is as follows:
wherein R = -CH3or-Ph; m and n are integers of 3-50.
The invention also discloses a carborane ceramic precursor system which comprises a carborane ceramic precursor, a solvent, a silane coupling agent and an epoxide; the chemical structural formula of the carborane ceramic precursor is as follows:
wherein R = -CH3or-Ph; m and n are integers of 3-50.
In the technical scheme, the solvent is a halogenated alkane solvent, the silane coupling agent is an epoxy silane coupling agent, the epoxide is a diisopropadiene diepoxide, and the mass concentration of the carborane ceramic precursor system is 1% ~ 40%.
The invention discloses a preparation method of a carborane ceramic precursor system for heat-resistant textiles based on carborane ceramic coatings, which comprises the steps of dissolving a carborane ceramic precursor in a halogenated alkane solvent, and then adding an epoxy silane coupling agent and a diisopropadiene diepoxide to prepare the carborane ceramic precursor system; the chemical structural formula of the carborane ceramic precursor is as follows:
wherein R = -CH3or-Ph; m and n are integers of 3-50.
In the technical scheme, the silane coupling agent is an epoxy silane coupling agent; the epoxide is a diisopropadiene diepoxide; the mass ratio of the carborane ceramic precursor to the epoxy silane coupling agent to the diisopropadiene diepoxide is 1: 0.05: 0.1.
The specific reaction formula for preparing the carborane ceramic precursor is as follows:
the novel carborane ceramic precursor disclosed by the invention contains cyclic silazane in the molecular main chain, can provide enough crosslinking reactivity and crosslinking degree, and can be well converted into a ceramic coating when being used for treating a textile coating; the coating is prepolymer, so the solution is easy to prepare, and a uniform, complete and controllable coating can be formed on the fiber surface of the treated fabric by controlling the concentration of the precursor solution, the treatment times and the like.
The preparation method comprises the steps of dropwise adding an ethynyl magnesium bromide Grignard reagent into a hydrocarbyl dichlorosilane solution under inert gas, reacting at 35-45 ℃, then dropwise adding a decaborane solution, reacting at 80-90 ℃ to obtain the hydrocarbyl silylene dicarboborane, dropwise adding an n-butyl lithium solution into the hydrocarbyl silylene dicarboborane solution under an ice-water bath condition under inert gas, reacting under the ice-water bath condition, then dropwise adding a dimethylchlorosilane solution, reacting under the ice-water bath condition, and reacting at room temperature to obtain the 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethylsilyl) dicarboborane, wherein the mass ratio of the hydrocarbyl dichlorosilane to the ethynyl magnesium bromide Grignard reagent to the decaborane is (0.2 ~) to (0.5 ~) to (0.1 ~), and the mass ratio of the hydrocarbyl silylene dicarboborane to the n-butyl lithium to the dimethylchlorosilane to ~ is (0.2.5) to ~).
The invention relates to a method for extracting a methanol gasoline from methanol gasoline, which comprises the steps of extracting an ethanol solvent with a solvent, wherein the extracting agent is diethyl ether, ethyl acetate, n-hexane or a solvent formed by mixing any two of the diethyl ether, the ethyl acetate and the n-hexane in any weight ratio, the drying agent is any one of anhydrous magnesium sulfate, anhydrous sodium sulfate and anhydrous calcium chloride, the aromatic hydrocarbon solvent is toluene, xylene or a mixed solvent formed by mixing the toluene and the xylene in any ratio, and the conditions for removing the extracting agent by rotary evaporation are that the temperature is 30 ~ 60 ℃ and the vacuum degree is 10 ~ 20 mm.
Compared with the prior art, the invention has the outstanding advantages that:
1. different from the ceramic precursor for coating treatment in the prior art, the novel carborane ceramic precursor disclosed by the invention takes annular trimethyl cyclotrisilazane as a framework support, the uniform reticular cross-linking structure provided by the chain link of the cyclotrisilazane can enable carborane to be more uniformly distributed on the surface of a fiber, and the double carborane sandwich structure is utilized to provide excellent heat resistance and thermal oxidation resistance.
2. The carborane ceramic precursor molecule main chain boron-containing element provided by the invention can increase the coating quality when being heated and oxidized, so that the quality loss caused by the thermal decomposition of the coating can be compensated, the cracks generated in the thermal decomposition process of the coating can be avoided, and the aramid fiber and the ceramic matrix interface can be more tightly combined, so that a better protection effect can be achieved.
3. The raw materials used by the novel carborane ceramic precursor disclosed by the invention are all commercially available raw materials, are wide in source, low in price and free of toxicity; the reaction condition is mild, the process is simple, the product is easy to purify, the disclosed novel carborane precursor is prepared by polymerizing industrial and commercially available raw materials of trivinyl trimethyl cyclotrisilazane and a nontoxic carborane compound, and the preparation method is simple and safe, has a good operation environment and is suitable for industrial scale-up production.
Drawings
FIG. 1 is a graph of the infrared absorption of a novel carborane ceramic precursor prepared in example one;
FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of the novel carborane ceramic precursor prepared in example one.
Detailed Description
The technical scheme of the invention is further explained by combining the drawings and the embodiment.
Example one
1. Synthesis of 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethylhydroxysilyl) dicarboborane
135 g of dehydrated tetrahydrofuran and 13.2 g of diphenyldichlorosilane are added into a 1000ml three-neck flask, after an experimental device is built, air in the device is firstly introduced, 25 g of ethynyl magnesium bromide Grignard reagent is dripped through a constant pressure dropping funnel, the dripping time is 30 minutes, the reaction temperature is set to be 40 ℃, the reaction time is 4 hours, a mixed solution of 6.2 g of decaborane, 78 g of acetonitrile and 178 g of tetrahydrofuran is simultaneously prepared, and after the reaction is carried out for 4 hours, the dripping time is 30 minutes through the constant pressure dropping funnel. After the completion of the dropwise addition, the reaction temperature was adjusted to 80 ℃ and the reaction time was adjusted to 48 hours. After the reaction is finished, the prepared mixed solution of 110 g of acetonitrile, 55 g of acetone, 36 g of concentrated hydrochloric acid and 50 g of deionized water is added for quenching, and the quenching time is 6 hours until no bubbles are generated. After quenching, the reaction solution was extracted with anhydrous ether, 200 g of which was added each time, 3 times. Combining the extracts, separating an oil layer, washing with deionized water to neutrality, adding 30 g of anhydrous magnesium sulfate, drying for 5 hours, finally filtering, and carrying out rotary evaporation at 45 ℃ and a vacuum degree of 20mmHg until the weight is constant to obtain 9.8g of bis-phenyl silylene dicarboborane.
17.82 g of dry tetrahydrofuran and 2.36 g of bis-phenyl-silylene dicarboborane are added into a 100ml three-neck flask, after an experimental device is built, air in the device is firstly introduced, the temperature of the solution in the three-neck flask is reduced to 0 ℃ under the ice bath condition, and then 6.00 g of 1.6M n-butyl lithium hexane solution is dripped through a constant pressure dropping funnel, the dripping time is 15 minutes, the reaction time is 2 hours, and the reaction temperature is kept below zero. After reacting for two hours, a mixed solution of 0.95 g of dimethylchlorosilane and 8.92 g of dry tetrahydrofuran is dropwise added under the ice-bath condition, the dropwise adding process is 15 minutes, and the reaction is continued under the condition of transferring to room temperature after reacting for 1 hour, and the reaction time is 24 hours.
After the reaction was completed, 20.58 g of a saturated ammonium chloride solution was added thereto for quenching for 12 hours. After quenching, extracting the reaction solution by using anhydrous ether, separating liquid, washing the reaction solution to be neutral by using deionized water, drying 4.00 g of anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation at 35 ℃ and under the vacuum degree of 20mmHg to constant weight to obtain the product 1,1 '-bis (phenyl) silylene-2, 2' -bis (dimethyl silicon-based) dicarboborane.
Preparing a buffer solution: 0.20 g of sodium hydroxide is added into 50.00g of deionized water to prepare 0.1 mol/L sodium hydroxide solution, 0.65 g of sodium dihydrogen phosphate monohydrate is added after dissolution, and the solution is stirred and dissolved.
A250 ml three-necked flask was charged with a buffer solution, 15.51 g of 1, 4-dioxane and 0.50 g
After an experimental device is built, 3.00 g of a prepared mixed solution of 1,1 '-bis (phenylsilyl-2, 2' -bis (dimethylsilyl) dicarboborane and 17.50 g of dehydrated toluene is dripped through a constant-pressure dropping funnel, the dripping time is 5 minutes, the reaction temperature is set to be 35 ℃, and the reaction time is 12 hours.
After the reaction is finished, the insoluble palladium-carbon catalyst is removed by suction filtration, and the filtrate is extracted by anhydrous ether, 20 g of anhydrous ether is added each time, and the extraction is carried out for 3 times. Combining the extracts, separating an oil layer, washing with deionized water to be neutral, adding 5 g of anhydrous magnesium sulfate, drying for 5 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and the vacuum degree of 20mmHg until the weight is constant to obtain the product 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane.
2. Synthesis of 1,3, 5-trimethyl-1, 3, 5-tris [ alpha ]β- (dimethylchlorosilyl) ethyl]Cyclotrisilazane
Adding 17.50 g of water-removed toluene solution, 1.27 g of trivinyl trimethyl cyclotrisilazane and 0.01 g of Kaster catalyst into a 100ml three-neck flask, building an experimental device, introducing nitrogen to remove air in the device, and dropwise adding a prepared mixed solution of 1.42 g of dimethylchlorosilane and 8.75 g of water-removed toluene through a constant-pressure dropping funnelDropwise adding for 5 minutes, reacting for 1 hour at 25 ℃, then heating to 75 ℃ and reacting for 4 hours, wherein the reaction solution becomes silver gray to obtain the product 1,3, 5-trimethyl-1, 3, 5-tris [ Delta ], [ beta ] -2β- (dimethylchlorosilyl) ethyl]And (4) performing the next reaction directly on the cyclotrisilazane.
3. Polycondensation reaction
13.00 g of anhydrous toluene, 3.07 g of 1,1 '-bis (phenylsilyl-2, 2' -bis (dimethylhydroxysilyl) dicarboborane and 1.02 g of triethylamine are added into a 100ml beaker and mixed uniformly for later use.
1,3, 5-trimethyl-1, 3, 5-tris [ alpha ], [ beta ] -produced in the above step 2β- (dimethylchlorosilyl) ethyl]And (2) dropwise adding the prepared carborane monomer solution into the cyclotrisilazane through a constant-pressure dropping funnel, wherein the dropwise adding time is 15 minutes, reacting at room temperature for 30 minutes, heating to 50 ℃, and reacting for 18 hours.
After the reaction is finished, naturally cooling to room temperature, carrying out suction filtration to remove insoluble triethylamine hydrochloride, extracting the filtrate by using anhydrous ether, separating liquid, washing the filtrate to be neutral by using deionized water, drying 5 g of anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and under the vacuum degree of 20mmHg to constant weight to obtain the novel carborane ceramic precursor.
Referring to the attached figure 1, the infrared absorption curve spectrum of the novel carborane ceramic precursor prepared according to the technical scheme of the embodiment is shown. As can be seen from the figure, 3379.83 cm-1The absorption peak is the stretching vibration peak of N-H; the B-H peak of carborane is 2563.46 cm-1At least one of (1) and (b); and 1031.58 cm-1At Si-O-Si cm-1The occurrence of polycondensation reaction is strongly confirmed by the stretching vibration peak of (2).
Referring to the attached figure 2, the new carborane ceramic precursor hydrogen nuclear magnetic resonance spectrum prepared according to the technical scheme of the embodiment is shown. As can be seen from the figure, 0.05-0.26 (m, Si-CH)3)；0.4-2.0(br, B-H)；7.2-7.7(d, ph-H)；2.27(d,N-H); 5.86-6.08(m, CH=CH2) (ii) a The synthesis of the polymer was confirmed in combination with the infrared absorption spectrum.
The molecular structural formula of the carborane ceramic precursor is as follows:
m and n are each an integer of 4 ~ 8
4. Coating treatment
Dissolving 12g of carborane ceramic precursor in 100g of dichloromethane solution to prepare a solution with the mass concentration of 0.12 g/ml, and adding 0.6g of epoxy silane coupling agent KH560 and 1.2g of diisopropadiene diepoxide (ERL-4269) for later use. Soaking the Kevlar aramid fabric in a carborane ceramic precursor system, and naturally drying at room temperature. Repeating the treatment for 3 times to obtain the aramid fiber fabric with 1-3 layers of coatings on the surface.
Performing a tensile test according to the national standard GB/1040.2-2006, wherein the tensile speed is 100mm/min, and the tensile strength of the untreated aramid fiber fabric is measured to be 55.9 MPa; the tensile strength of the aramid fiber subjected to coating treatment for 1 time is 56.7MPa, which is improved by 1.5%; after the coating is treated for 2 times, the tensile strength of the aramid fiber is 56.3MPa, which is improved by 0.8%; after the coating is treated for 3 times, the tensile strength of the aramid fiber is 56.0MPa, which is improved by 0.2 percent.
The heat-resistant stability of the aramid fiber before and after the treatment is tested, and it can be seen that the untreated aramid fiber is completely degraded in 30 minutes at 400 ℃, and the aramid fiber fabric treated by 3 times of coating has a mass residue of 99% even after being heated to 500 ℃ and baked for 2 hours.
Example two
1. Synthesis of 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethylhydroxysilyl) dicarboborane
135 g of dehydrated tetrahydrofuran and 13.2 g of diphenyldichlorosilane are added into a 1000ml three-neck flask, after an experimental device is built, air in the device is firstly introduced, 25 g of ethynyl magnesium bromide Grignard reagent is dripped through a constant pressure dropping funnel, the dripping time is 30 minutes, the reaction temperature is set to be 40 ℃, the reaction time is 4 hours, a mixed solution of 6.2 g of decaborane, 78 g of acetonitrile and 178 g of tetrahydrofuran is simultaneously prepared, and after the reaction is carried out for 4 hours, the dripping time is 30 minutes through the constant pressure dropping funnel. After the end of the dropwise addition, the reaction temperature was adjusted to 86 ℃ and the reaction time was adjusted to 48 hours. After the reaction is finished, the prepared mixed solution of 110 g of acetonitrile, 55 g of acetone, 36 g of concentrated hydrochloric acid and 50 g of deionized water is added for quenching, and the quenching time is 6 hours until no bubbles are generated. After quenching, the reaction solution was extracted with anhydrous ether, 200 g of which was added each time, 3 times. Combining the extracts, separating an oil layer, washing with deionized water to neutrality, adding 30 g of anhydrous magnesium sulfate, drying for 5 hours, finally filtering, and carrying out rotary evaporation at 45 ℃ and a vacuum degree of 20mmHg until the weight is constant to obtain 9.8g of bis-phenyl silylene dicarboborane.
35.64 g of dry tetrahydrofuran and 4.75 g of bis-phenyl-silylene dicarboborane are added into a 250ml three-neck flask, after an experimental device is built, air in the device is firstly introduced, the temperature of the solution in the three-neck flask is reduced to 0 ℃ under the ice bath condition, 12.50 g of 1.6M n-butyl lithium hexane solution is dripped through a constant pressure dropping funnel, the dripping time is 20 minutes, the reaction time is 4 hours, and the reaction temperature is kept below zero. After 4 hours of reaction, a mixed solution of 1.92 g of dimethylchlorosilane and 17.85 g of dry tetrahydrofuran was added dropwise under the ice bath condition, the dropwise addition was carried out for 20 minutes, and the reaction was continued at room temperature after 1 hour of reaction for 24 hours.
After the reaction was completed, 41.16 g of a saturated ammonium chloride solution was added thereto to quench for 20 hours. After quenching, extracting the reaction solution by using anhydrous ether, separating liquid, washing the reaction solution to be neutral by using deionized water, drying 10 g of anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation at 35 ℃ and under the vacuum degree of 20mmHg to constant weight to obtain the product 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethylsilyl) dicarboborane.
Preparing a buffer solution: 0.40 g of sodium hydroxide is added into 100.00g of deionized water to prepare 0.10 mol/L sodium hydroxide solution, 1.30 g of sodium dihydrogen phosphate monohydrate is added after dissolution, and the solution is stirred and dissolved.
A250 ml three-neck flask is firstly added with a buffer solution, 32.00 g of 1, 4-dioxane and 1.50 g of palladium carbon catalyst, after an experimental device is built, a prepared mixed solution of 6.00 g of 1,1 '-bis (phenyl silicon methylene) -2, 2' -bis (dimethyl silicon base) dicarboborane and 35.50 g of water-removed toluene is dripped through a constant pressure dropping funnel, the dripping time is 5 minutes, the reaction temperature is set to be 35 ℃, and the reaction time is 12 hours.
After the reaction is finished, the insoluble palladium-carbon catalyst is removed by suction filtration, and the filtrate is extracted by anhydrous ether, 40 g of anhydrous ether is added each time, and the extraction is carried out for 5 times. Combining the extracts, separating an oil layer, washing with deionized water to be neutral, adding 15 g of anhydrous magnesium sulfate, drying for 5 hours, finally filtering, and carrying out rotary evaporation at 60 ℃ and a vacuum degree of 20mmHg until the weight is constant to obtain the product 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane.
2. Synthesis of 1,3, 5-trimethyl-1, 3, 5-tris [ alpha ]β- (dimethylchlorosilyl) ethyl]Cyclotrisilazane
Adding 35.00 g of water-removed toluene solution, 2.54 g of trivinyl trimethyl cyclotrisilazane and 0.02 g of Kaster catalyst into a 250ml three-neck flask, building an experimental device, introducing nitrogen to remove air in the device, dropwise adding a prepared mixed solution of 2.84 g of dimethylchlorosilane and 17.75 g of water-removed toluene through a constant-pressure dropping funnel for 10 minutes, reacting at 35 ℃ for 1 hour, then heating to 75 ℃ for 4 hours, and changing the reaction liquid into silver gray to obtain a product 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane, and directly carrying out the next reaction.
3. Polycondensation reaction
26.00 g of anhydrous toluene, 6.54 g of 1,1 '-bis (phenylsilyl-2, 2' -bis (dimethylhydroxysilyl) dicarboborane and 2.04 g of triethylamine are added into a 250ml beaker and mixed uniformly for later use.
And (3) dropwise adding the prepared carborane monomer solution into the 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane obtained in the step (2) through a constant-pressure dropping funnel for 30 minutes, reacting at room temperature for 1 hour, heating to 55 ℃, and reacting for 24 hours.
After the reaction is finished, naturally cooling to room temperature, carrying out suction filtration to remove insoluble triethylamine hydrochloride, extracting the filtrate by using anhydrous ether, separating liquid, washing the filtrate to be neutral by using deionized water, drying 10 g of anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and under the vacuum degree of 15mmHg to constant weight to obtain the novel carborane ceramic precursor.
m and n are each an integer of 5 ~ 10
4. Coating treatment
Dissolving 12g of carborane ceramic precursor in 100ml of dichloromethane solution to prepare a solution with the mass concentration of 0.12 g/ml, and adding 0.6g of epoxy silane coupling agent KH560 and 1.2g of diisopropadiene diepoxide (ERL-4269) for later use. Soaking the aramid fiber fabric in a carborane ceramic precursor system, and naturally drying at room temperature. And repeating the treatment for 5 times to obtain the aramid fiber fabric with 5 coatings on the surface.
Performing a tensile test according to the national standard GB/1040.2-2006, wherein the tensile speed is 100mm/min, and the tensile strength of the untreated aramid fiber fabric is measured to be 55.9 MPa; the tensile strength of the aramid fiber subjected to coating treatment for 1 time is 56.6MPa, which is improved by 1.7%; after the coating is treated for 2 times, the tensile strength of the aramid fiber is 56.3MPa, which is improved by 0.7%; after the coating is treated for 5 times, the tensile strength of the aramid fiber is 56.0MPa, which is improved by 0.1%.
The heat-resistant stability of the aramid fiber before and after the treatment is tested, and it can be seen that the untreated aramid fiber is completely degraded in 30 minutes at 400 ℃, and the aramid fiber fabric treated by 5 times of coating has a mass residue of 99% even after being heated to 500 ℃ and baked for 2 hours.
EXAMPLE III
1. Synthesis of 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethylhydroxysilyl) dicarboborane
135 g of dehydrated tetrahydrofuran and 13.2 g of diphenyldichlorosilane are added into a 1000ml three-neck flask, after an experimental device is built, air in the device is firstly introduced, 25 g of ethynyl magnesium bromide Grignard reagent is dripped through a constant pressure dropping funnel, the dripping time is 30 minutes, the reaction temperature is set to be 40 ℃, the reaction time is 4 hours, a mixed solution of 6.2 g of decaborane, 78 g of acetonitrile and 178 g of tetrahydrofuran is simultaneously prepared, and after the reaction is carried out for 4 hours, the dripping time is 30 minutes through the constant pressure dropping funnel. After the completion of the dropwise addition, the reaction temperature was adjusted to 80 ℃ and the reaction time was adjusted to 48 hours. After the reaction is finished, the prepared mixed solution of 110 g of acetonitrile, 55 g of acetone, 36 g of concentrated hydrochloric acid and 50 g of deionized water is added for quenching, and the quenching time is 6 hours until no bubbles are generated. After quenching, the reaction solution was extracted with anhydrous ether, 200 g of which was added each time, 3 times. Combining the extracts, separating an oil layer, washing with deionized water to neutrality, adding 30 g of anhydrous magnesium sulfate, drying for 5 hours, finally filtering, and carrying out rotary evaporation at 45 ℃ and a vacuum degree of 20mmHg until the weight is constant to obtain 9.8g of bis-phenyl silylene dicarboborane.
71.28 g of dry tetrahydrofuran and 9.55 g of bis-phenyl silylene dicarboborane are added into a 1000ml three-neck flask, after an experimental device is built, air in the device is firstly introduced to remove air, the temperature of the solution in the three-neck flask is reduced to 0 ℃ under the ice bath condition, 25.50 g of 1.6M n-butyl lithium hexane solution is dripped through a constant pressure dropping funnel, the dripping time is 60 minutes, the reaction time is 8 hours, and the reaction temperature is kept below zero. After 8 hours of reaction, a mixed solution of 3.95 g of dimethylchlorosilane and 35.75 g of dry tetrahydrofuran was added dropwise under the ice bath condition, the dropwise addition was carried out for 30 minutes, and the reaction was continued at room temperature after 2 hours of reaction for 24 hours.
After the reaction was completed, 82.32 g of a saturated ammonium chloride solution was added thereto for quenching for 20 hours. After quenching, extracting the reaction solution by using anhydrous ether, separating liquid, washing the reaction solution to be neutral by using deionized water, drying 20 g of anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation at 40 ℃ and under the vacuum degree of 20mmHg to constant weight to obtain the product 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethylsilyl) dicarboborane.
Preparing a buffer solution: 0.80 g of sodium hydroxide is added into 200.00g of deionized water to prepare 0.10 mol/L sodium hydroxide solution, 2.60 g of sodium dihydrogen phosphate monohydrate is added after dissolution, and the solution is stirred and dissolved.
A250 ml three-neck flask is firstly added with a buffer solution, 64.00 g of 1, 4-dioxane and 3.50 g of palladium carbon catalyst, after an experimental device is built, a prepared mixed solution of 12.50 g of 1,1 '-bis (phenyl silicon methylene) -2, 2' -bis (dimethyl silicon base) dicarboborane and 71.50 g of toluene with water is dripped through a constant pressure dropping funnel, the dripping time is 30 minutes, the reaction temperature is set to be 55 ℃, and the reaction time is 12 hours.
After the reaction is finished, the insoluble palladium-carbon catalyst is removed by suction filtration, and the filtrate is extracted by anhydrous ether, 100g of anhydrous ether is added each time, and the extraction is carried out for 3 times. Combining the extracts, separating an oil layer, washing with deionized water to be neutral, adding 50 g of anhydrous magnesium sulfate, drying for 5 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and the vacuum degree of 20mmHg until the weight is constant to obtain the product 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane.
2. Synthesis of 1,3, 5-trimethyl-1, 3, 5-tris [ alpha ]β- (dimethylchlorosilyl) ethyl]Cyclotrisilazane
75.50 g of water-removed toluene solution, 5.25 g of trivinyl trimethyl cyclotrisilazane and 0.05 g of Kaster catalyst are added into a 1000ml three-neck flask, after an experimental device is built, nitrogen is introduced to remove air in the device, then a prepared mixed solution of 5.75 g of dimethylchlorosilane and 35.50 g of water-removed toluene is dripped through a constant-pressure dropping funnel, the dripping time is 30 minutes, the mixture reacts for 1 hour at the temperature of 45 ℃, then the temperature is raised to 75 ℃ for 5 hours, the reaction liquid turns silver gray, and a product 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane is obtained and directly enters the next reaction.
3. Polycondensation reaction
55.00 g of anhydrous toluene, 6.50 g of 1,1 '-bis (phenylsilyl-2, 2' -bis (dimethylhydroxysilyl) dicarboborane and 2.50 g of triethylamine are added into a 1000ml beaker and mixed uniformly for later use.
And (3) dropwise adding the prepared carborane monomer solution into the 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane obtained in the step (2) through a constant-pressure dropping funnel, wherein the dropwise adding time is 45 minutes, reacting at room temperature for 120 minutes, then heating to 55 ℃, and reacting for 36 hours.
After the reaction is finished, naturally cooling to room temperature, carrying out suction filtration to remove insoluble triethylamine hydrochloride, extracting the filtrate with anhydrous ether, separating liquid, washing with deionized water to be neutral, drying with 50 g of anhydrous magnesium sulfate for 12 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and under the vacuum degree of 20mmHg to constant weight to obtain the product, namely the carborane ceramic precursor. The molecular structural formula of the carborane ceramic precursor is as follows:
m and n are each an integer of 4 ~ 6
4. Coating treatment
Dissolving 12g of carborane ceramic precursor in 100g of dichloromethane solution to prepare a solution with the mass concentration of 0.12 g/ml, and adding 0.6g of epoxy silane coupling agent KH560 and 1.2g of diisopropadiene diepoxide (ERL-4269) for later use. Soaking the aramid fiber fabric in a carborane ceramic precursor system, and naturally drying at room temperature. Repeating the treatment for 3 times to obtain the aramid fiber fabric with 1-3 layers of coatings on the surface.
The tensile strength of the aramid fiber subjected to coating treatment for 1 time is 56.7MPa, which is improved by 1.4%; after the coating is treated for 2 times, the tensile strength of the aramid fiber is 56.3MPa, which is improved by 0.8%; after the coating is treated for 3 times, the tensile strength of the aramid fiber is 56.1MPa, which is improved by 0.3 percent.
The heat-resistant stability of the aramid fiber before and after the treatment is tested, and it can be seen that the untreated aramid fiber is completely degraded in 30 minutes at 400 ℃, and the aramid fiber fabric treated by 3 times of coating has a mass residue of 89% even after being heated to 550 ℃ and baked for 2 hours.
Example four
1. Synthesis of 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethylhydroxysilyl) dicarboborane
145.50 g of dry tetrahydrofuran and 19.32 g of bis-phenyl-silylene dicarboborane (example one) were put into a 2000ml three-neck flask, after setting up the experimental apparatus, the air in the apparatus was purged first, the temperature of the solution in the three-neck flask was lowered to 0 ℃ under ice bath condition, and then 55.25 g of 1.6M n-butyllithium hexane solution was dropped through a constant pressure dropping funnel for 120 minutes for 8 hours while maintaining the reaction temperature at zero. After 8 hours of reaction, a mixed solution of 7.68 g of dimethylchlorosilane and 71.45 g of dry tetrahydrofuran was added dropwise under the ice bath condition, the dropwise addition was carried out for 60 minutes, and the reaction was continued at room temperature after 2 hours of reaction for 36 hours.
After the reaction was completed, 164.64 g of a saturated ammonium chloride solution was added thereto for quenching for 20 hours. After quenching, extracting the reaction solution by using anhydrous ethyl acetate, separating liquid, washing the reaction solution to be neutral by using deionized water, drying 40 g of anhydrous magnesium sulfate for 12 hours, finally filtering, and carrying out rotary evaporation at the temperature of 35 ℃ and the vacuum degree of 10mmHg to constant weight to obtain the product 1,1 '-bis (phenyl silyl) -2, 2' -bis (dimethyl silicon base) dicarboborane.
Preparing a buffer solution: 1.60 g of sodium hydroxide is added into 400.00g of deionized water to prepare 0.10 mol/L sodium hydroxide solution, after dissolution, 5.20 g of sodium dihydrogen phosphate monohydrate is added, and the solution is stirred and dissolved.
A2000 ml three-neck flask is firstly added with a buffer solution, 135.50 g of 1, 4-dioxane and 6.50 g of palladium carbon catalyst, after an experimental device is built, a prepared mixed solution of 24.30 g of 1,1 '-bis (phenyl silicon methylene-2, 2' -bis (dimethyl silicon base) dicarboborane and 142.50 g of toluene with water removal is dripped through a constant pressure dropping funnel, the dripping time is 5 minutes, the reaction temperature is set to be 35 ℃, and the reaction time is 12 hours.
After the reaction is finished, filtering to remove the insoluble palladium-carbon catalyst, extracting the filtrate by using anhydrous n-hexane, adding 40 g of anhydrous n-hexane each time, and extracting for 5 times. Combining the extracts, separating an oil layer, washing with deionized water to be neutral, adding 100g of anhydrous magnesium sulfate, drying for 12 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and the vacuum degree of 15mmHg until the weight is constant to obtain the product 1,1 '-bis-phenyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane.
2. Synthesis of 1,3, 5-trimethyl-1, 3, 5-tris [ alpha ]β- (dimethylchlorosilyl) ethyl]Cyclotrisilazane
145.00 g of water-removed toluene solution, 10.50 g of trivinyl trimethyl cyclotrisilazane and 0.10 g of Karsted catalyst are added into a 2000ml three-neck flask, after an experimental device is built, nitrogen is introduced to remove air in the device, then a prepared mixed solution of 11.52 g of dimethylchlorosilane and 71.50 g of water-removed toluene is dripped through a constant-pressure dropping funnel, the dripping time is 120 minutes, the mixture reacts for 2 hours at 35 ℃, then the temperature is raised to 75 ℃ and the reaction solution reacts for 10 hours, the reaction solution is changed into silver gray, and a product 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane is obtained and directly enters the next reaction.
3. Polycondensation reaction
105.50 g of anhydrous toluene, 27.80 g of 1,1 '-diphenylsilylene-2, 2' -bis (dimethylhydroxysilyl) dicarbaborane and 8.53 g of triethylamine are added to a 2000ml beaker and mixed uniformly for later use.
And (3) dropwise adding the prepared carborane monomer solution into the 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane obtained in the step (2) through a constant-pressure dropping funnel, wherein the dropwise adding time is 120 minutes, reacting for 4 hours at room temperature, heating to 55 ℃, and reacting for 48 hours.
After the reaction is finished, naturally cooling to room temperature, carrying out suction filtration to remove insoluble triethylamine hydrochloride, extracting the filtrate by using anhydrous n-hexane, separating liquid, washing the filtrate to be neutral by using deionized water, drying the filtrate for 5 hours by using 100g of anhydrous sodium sulfate, finally filtering, and carrying out rotary evaporation at 55 ℃ and under the vacuum degree of 15mmHg to constant weight to obtain the product, namely the novel carborane ceramic precursor.
The molecular structural formula of the carborane ceramic precursor is as follows:
m and n are each an integer of 6 ~ 12
4. Coating treatment
Dissolving 12g of carborane ceramic precursor in 100g of dichloromethane solution to prepare a solution with the mass concentration of 0.12 g/ml, and adding 0.6g of epoxy silane coupling agent KH560 and 1.2g of diisopropadiene diepoxide (ERL-4269) for later use. Soaking the aramid fiber fabric in a carborane ceramic precursor system, and naturally drying at room temperature. Repeating the treatment for 3 times to obtain the aramid fiber fabric with 1-3 layers of coatings on the surface.
The tensile strength of the aramid fiber subjected to coating treatment for 1 time is 56.8MPa, which is improved by 1.6%; after the coating is treated for 2 times, the tensile strength of the aramid fiber is 56.3MPa, which is improved by 0.8%; after the coating is treated for 3 times, the tensile strength of the aramid fiber is 56.0MPa, which is improved by 0.2 percent.
The heat-resistant stability of the aramid fiber before and after the treatment is tested, and it can be seen that the untreated aramid fiber is completely degraded in 30 minutes at 400 ℃, and the aramid fiber fabric treated by 3 times of coating has a mass residue of 69% even after being heated to 600 ℃ and baked for 2 hours.
EXAMPLE five
1. Synthesis of 1,1 '-methylphenylsilylene-2, 2' -bis (dimethylhydroxysilyl) dicarboborane
135 g of dehydrated tetrahydrofuran and 9.6 g of methyl phenyl dichlorosilane are added into a 1000ml three-neck flask, after an experimental device is built, air in the device is firstly introduced, 22 g of ethynyl magnesium bromide Grignard reagent is dripped through a constant pressure dropping funnel, the dripping time is 35 minutes, the reaction temperature is set to be 40 ℃, the reaction time is 4 hours, a mixed solution of 6.2 g of decaborane, 78 g of acetonitrile and 178 g of tetrahydrofuran is simultaneously prepared, and after 4 hours of reaction, the dripping time is 35 minutes through the constant pressure dropping funnel. After the completion of the dropwise addition, the reaction temperature was adjusted to 80 ℃ and the reaction time was adjusted to 48 hours.
After the reaction is finished, adding a prepared mixed solution of 110 g of acetonitrile, 55 g of acetone, 36 g of concentrated hydrochloric acid and 50 g of deionized water for quenching, wherein the quenching time is 6 hours until no bubbles are generated, after the quenching is finished, extracting the reaction solution by using anhydrous ether, separating liquid, washing the reaction solution to be neutral by using deionized water, drying the reaction solution by using anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation at 30 ℃ and a vacuum degree of 15mmHg until the weight is constant to obtain 8.8g of the product of the methyl phenyl silicon methylene dicarboborane.
17.82 g of dry tetrahydrofuran and 2.36 g of methylphenylsilyldicarbaborane are added into a 100ml three-neck flask, after an experimental device is built, air in the device is firstly introduced to remove air in the device, the temperature of the solution in the three-neck flask is reduced to 0 ℃ under the ice bath condition, and then 6.00 g of 1.6M n-butyllithium hexane solution is dripped through a constant pressure dropping funnel, the dripping time is 15 minutes, the reaction time is 2 hours, and the reaction temperature is kept below zero. After reacting for two hours, a mixed solution of 0.95 g of dimethylchlorosilane and 8.92 g of dry tetrahydrofuran is dropwise added under the ice-bath condition, the dropwise adding process is 15 minutes, and the reaction is continued under the condition of transferring to room temperature after reacting for 1 hour, and the reaction time is 24 hours.
After the reaction was completed, 20.58 g of a saturated ammonium chloride solution was added thereto for quenching for 12 hours. After quenching, extracting the reaction solution by using anhydrous ether, separating liquid, washing the reaction solution to be neutral by using deionized water, drying 4.00 g of anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation to constant weight at 35 ℃ and under the vacuum degree of 20mmHg to obtain the product 1,1 '-methylphenylsilylene-2, 2' -bis (dimethylsilyl) dicarboborane.
Preparing a buffer solution: 0.20 g of sodium hydroxide is added into 50.00g of deionized water to prepare 0.1 mol/L sodium hydroxide solution, 0.65 g of sodium dihydrogen phosphate monohydrate is added after dissolution, and the solution is stirred and dissolved.
A250 ml three-necked flask was charged with a buffer solution, 15.51 g of 1, 4-dioxane and 0.50 g
After an experimental device is built, 3.00 g of a prepared mixed solution of 1,1 '-methylphenylsilyl-2, 2' -bis (dimethylsilyl) dicarboborane and 17.50 g of dehydrated toluene is dripped through a constant-pressure dropping funnel, the dripping time is 5 minutes, the reaction temperature is set to be 35 ℃, and the reaction time is 12 hours.
After the reaction is finished, filtering to remove the insoluble palladium-carbon catalyst, extracting the filtrate with anhydrous ethyl acetate each time
20 g of anhydrous ethyl acetate was added thereto, and the mixture was extracted 3 times. Combining the extraction liquids, separating an oil layer, washing with deionized water to be neutral, adding 5 g of anhydrous calcium chloride, drying for 5 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and the vacuum degree of 20mmHg until the weight is constant to obtain the product 1,1 '-methyl phenyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane.
2. Synthesis of 1,3, 5-trimethyl-1, 3, 5-tris [ alpha ]β- (dimethylchlorosilyl) ethyl]Cyclotrisilazane
17.50 g of a water-removed toluene solution, 1.27 g of trivinyl trimethyl cyclotrisilazane and 0.01 g of a Kaster catalyst are added into a 100ml three-neck flask, after an experimental device is built, nitrogen is introduced to remove air in the device, then a prepared mixed solution of 1.42 g of dimethylchlorosilane and 8.75 g of water-removed toluene is dripped through a constant-pressure dropping funnel, the dripping time is 5 minutes, the mixture reacts for 1 hour at 25 ℃, then the temperature is raised to 75 ℃ and the reaction solution reacts for 4 hours, the reaction solution is changed into silver gray, and a product 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane is obtained and directly enters the next reaction.
3. Polycondensation reaction
13.00 g of anhydrous toluene, 3.67 g of 1,1 '-methylphenylsilyl-2, 2' -bis (dimethylhydroxysilyl) dicarbaborane and 1.02 g of triethylamine are added into a 100ml beaker and mixed uniformly for later use.
And (3) dropwise adding the prepared carborane monomer solution into the 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane obtained in the step (2) through a constant-pressure dropping funnel, wherein the dropwise adding time is 15 minutes, reacting at room temperature for 30 minutes, then heating to 50 ℃, and reacting for 18 hours.
After the reaction is finished, naturally cooling to room temperature, carrying out suction filtration to remove insoluble triethylamine hydrochloride, extracting the filtrate by using anhydrous ether, separating liquid, washing the filtrate to be neutral by using deionized water, drying 5 g of anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and under the vacuum degree of 20mmHg to constant weight to obtain the product, namely the novel carborane ceramic precursor.
The molecular structural formula of the carborane ceramic precursor is as follows:
m and n are each an integer of 5 ~ 12
4. Coating treatment
Dissolving 12g of carborane ceramic precursor in 100g of dichloromethane solution to prepare a solution with the mass concentration of 0.12 g/ml, and adding 0.6g of epoxy silane coupling agent KH560 and 1.2g of diisopropadiene diepoxide (ERL-4269) for later use. Soaking the aramid fiber fabric in a carborane ceramic precursor system, and naturally drying at room temperature. Repeating the treatment for 3 times to obtain the aramid fiber fabric with 1-3 layers of coatings on the surface.
Performing a tensile test according to the national standard GB/1040.2-2006, wherein the tensile speed is 100mm/min, and the tensile strength of the untreated aramid fiber fabric is measured to be 55.9 MPa; the tensile strength of the aramid fiber subjected to coating treatment for 1 time is 56.7MPa, which is improved by 1.5%; after the coating is treated for 2 times, the tensile strength of the aramid fiber is 56.3MPa, which is improved by 0.8%; after the coating is treated for 3 times, the tensile strength of the aramid fiber is 56.0MPa, which is improved by 0.2 percent.
The heat-resistant stability of the aramid fiber before and after the treatment is tested, and it can be seen that the untreated aramid fiber is completely degraded in 30 minutes at 400 ℃, and the aramid fiber fabric treated by 3 times of coating has a mass residue of 99% even after being heated to 500 ℃ and baked for 2 hours.
EXAMPLE six
1. Synthesis of 1,1 '-methylphenylsilylene-2, 2' -bis (dimethylhydroxysilyl) dicarboborane
35.64 g of dry tetrahydrofuran and 4.72 g of methylphenylsilyldicarbaborane (example five) were put into a 250ml three-neck flask, after setting up an experimental apparatus, air in the apparatus was purged first, the temperature of the solution in the three-neck flask was lowered to 0 ℃ under ice bath conditions, and then 12.50 g of a 1.6M n-butyllithium hexane solution was dropped through a constant pressure dropping funnel for 30 minutes for 3 hours while maintaining the reaction temperature at zero. After reacting for 3 hours, a mixed solution of 1.95 g of dimethylchlorosilane and 17.85 g of dry tetrahydrofuran is dropwise added under the ice bath condition, the dropwise adding process is 30 minutes, and the reaction is continued under the condition of transferring to room temperature after reacting for 2 hours, wherein the reaction time is 18 hours.
After the reaction was completed, 41.16 g of a saturated ammonium chloride solution was added thereto to quench for 12 hours. After quenching, extracting the reaction solution by using anhydrous ethyl acetate, separating, washing by using deionized water until the reaction solution is neutral, drying by using 10.00 g of anhydrous magnesium sulfate for 5 hours, finally filtering, and carrying out rotary evaporation at 40 ℃ and under the vacuum degree of 20mmHg until the reaction solution is constant in weight to obtain the product 1,1 '-methylphenylsilyl-2, 2' -bis (dimethylsilyl) dicarboborane.
Preparing a buffer solution: 0.40 g of sodium hydroxide is added into 100.00g of deionized water to prepare 0.1 mol/L sodium hydroxide solution, 1.30 g of sodium dihydrogen phosphate monohydrate is added after dissolution, and the solution is stirred and dissolved.
A250 ml three-necked flask was charged with the buffer solution, 32.50 g of 1, 4-dioxane and 1.50 g
The preparation method comprises the following steps of (1) building an experimental device, dropwise adding a prepared mixed solution of 6.50 g of 1,1 '-methylphenylsilylene-2, 2' -bis (dimethylsilyl) dicarboborane and 35.50 g of water-removed toluene through a constant-pressure dropping funnel, wherein the dropwise adding time is 15 minutes, the reaction temperature is set to be 35 ℃, and the reaction time is 12 hours.
After the reaction is finished, filtering to remove the insoluble palladium-carbon catalyst, extracting the filtrate with anhydrous ethyl acetate each time
20 g of anhydrous ethyl acetate was added thereto, and the mixture was extracted 5 times. Combining the extraction liquids, separating an oil layer, washing with deionized water to be neutral, adding 10 g of anhydrous calcium chloride, drying for 5 hours, finally filtering, and carrying out rotary evaporation at 55 ℃ and the vacuum degree of 15mmHg until the weight is constant to obtain the product 1,1 '-methyl phenyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane.
2. Synthesis of 1,3, 5-trimethyl-1, 3, 5-tris[β- (dimethylchlorosilyl) ethyl]Cyclotrisilazane
Adding 35.50 g of a water-removed toluene solution, 2.52 g of trivinyl trimethyl cyclotrisilazane and 0.04 g of a Kaster catalyst into a 250ml three-neck flask, building an experimental device, introducing nitrogen to remove air in the device, dropwise adding a prepared mixed solution of 2.85 g of dimethylchlorosilane and 16.50 g of water-removed toluene through a constant-pressure dropping funnel for 15 minutes, reacting at 35 ℃ for 1 hour, then heating to 65 ℃ for 5 hours, and changing the reaction liquid into silver gray to obtain a product 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chlorosilane base) ethyl ] cyclotrisilazane, and directly carrying out the next reaction.
3. Polycondensation reaction
26.50 g of anhydrous toluene, 6.81 g of 1,1 '-methylphenylsilylene-2, 2' -bis (dimethylhydroxysilyl) dicarbaborane and 2.42 g of triethylamine are added into a 250ml beaker and mixed uniformly for later use.
And (3) dropwise adding the prepared carborane monomer solution into the 1,3, 5-trimethyl-1, 3, 5-tris [ beta- (dimethyl chloro silicon base) ethyl ] cyclotrisilazane obtained in the step (2) through a constant-pressure dropping funnel for 20 minutes, reacting at room temperature for 50 minutes, heating to 50 ℃, and reacting for 24 hours.
And after the reaction is finished, naturally cooling to room temperature, carrying out suction filtration to remove insoluble triethylamine hydrochloride, extracting the filtrate by using anhydrous n-hexane, separating, washing the filtrate to be neutral by using deionized water, drying the filtrate for 5 hours by using 10 g of anhydrous sodium sulfate, finally filtering, and carrying out rotary evaporation at 55 ℃ and under the vacuum degree of 20mmHg to constant weight to obtain the carborane ceramic precursor.
The molecular structural formula of the carborane ceramic precursor is as follows:
m and n are each an integer of 6 ~ 12
4. Coating treatment
Dissolving 12g of carborane ceramic precursor in 100g of dichloromethane solution to prepare a solution with the mass concentration of 0.12 g/ml, and adding 0.6g of epoxy silane coupling agent KH560 and 1.2g of diisopropadiene diepoxide (ERL-4269) for later use. Soaking the aramid fiber fabric in a carborane ceramic precursor system, and naturally drying at room temperature. Repeating the treatment for 3 times to obtain the aramid fiber fabric with 1-3 layers of coatings on the surface.
The tensile strength of the aramid fiber subjected to coating treatment for 1 time is 56.7MPa, which is improved by 1.5%; after the coating is treated for 2 times, the tensile strength of the aramid fiber is 56.4MPa, which is improved by 0.9%; after the coating is treated for 3 times, the tensile strength of the aramid fiber is 56.0MPa, which is improved by 0.2 percent.
The heat-resistant stability of the aramid fiber before and after the treatment is tested, and it can be seen that the untreated aramid fiber is completely degraded in 30 minutes at 400 ℃, and the aramid fiber fabric treated by 3 times of coating has a mass residue of 99% even after being heated to 500 ℃ and baked for 2 hours.
After the treatment of the invention, the heat-resistant stability of the aramid fiber is greatly improved, the mechanical property is not reduced, the flexibility is particularly good, and the carborane ceramic can be bonded with a high-temperature resistant adhesive, so that the bonding is easy, and the problem that the existing high-temperature resistant textile is difficult to bond is solved.
Claims (6)
1. A carborane ceramic coating-based heat resistant textile, comprising an aramid textile and a carborane ceramic coating; the carborane ceramic is prepared from a carborane ceramic precursor; the chemical structural formula of the carborane ceramic precursor is as follows:
wherein R = -CH3or-Ph; m and n are integers of 3-50.
2. The carborane ceramic coating-based heat-resistant textile according to claim 1, wherein said carborane ceramic-based heat-resistant textile is prepared by a method comprising the steps of:
(1) 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane is used as a raw material and reacts under an alkaline condition and a metal catalyst to prepare the 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane;
(2) the 1,3, 5-trimethyl-1, 3, 5-tri- (tert-butyl-phenyl) -trisilazane is prepared from dimethylchlorosilane and trivinyl trimethyl cyclotrisilazane by reaction under the action of metal catalystβ- (dimethylchlorosilyl) ethyl]A cyclotrisilazane;
(3) 1,1 ' -hydrocarbon silicon methylene-2, 2 ' -bis (dimethyl hydroxyl silicon base) dicarboborane, 1,3, 5-trimethyl-1, 3, 5-tri [ alpha ], [ beta ] -methyl-2, 2 ' -bis (dimethyl hydroxyl silicon base)β- (dimethylchlorosilyl) ethyl]Preparing a carborane ceramic precursor by using cyclotrisilazane as a raw material in the presence of triethylamine;
(4) preparing a carborane ceramic precursor system by taking a carborane ceramic precursor, a solvent, a silane coupling agent and an epoxide as raw materials;
(5) soaking the textile in a carborane ceramic precursor system; the drying treatment results in a heat resistant textile based on a carborane ceramic coating.
3. Heat resistant textile based on carborane ceramic coatings according to claim 2,
mixing sodium hydroxide with water, adding sodium dihydrogen phosphate monohydrate, mixing to prepare a buffer solution, and adding an ether solvent and a metal catalyst; then adding aromatic hydrocarbon solution of 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethyl silicon base) dicarboborane to react to prepare 1,1 '-hydrocarbyl silylene-2, 2' -bis (dimethyl hydroxyl silicon base) dicarboborane;
adding a metal catalyst into a trivinyl trimethyl cyclotrisilazane arene solution in an inert atmosphere; then adding a dimethyl chlorosilane aromatic hydrocarbon solution; reaction to prepare 1,3, 5-trimethyl-1, 3, 5-tris [ alpha ], [ beta ] -aβ- (dimethylchlorosilyl) ethyl]A cyclotrisilazane;
step (3) is to contain triethylamine1,1 '-Hydroxysilylene-2, 2' -bis (dimethylhydroxysilyl) dicarboborane aromatic hydrocarbon solution of (1, 3, 5-trimethyl-1, 3, 5-tris [ ])β- (dimethylchlorosilyl) ethyl]Reacting in cyclotrisilazane to prepare a carborane ceramic precursor;
dissolving a carborane ceramic precursor in a halogenated alkane solvent, and then adding an epoxy silane coupling agent and a diisopropadiene diepoxide to prepare a carborane ceramic precursor system;
and (5) soaking the textile in the carborane ceramic precursor system for 0.5 ~ 1 hours, and air-drying at room temperature to obtain the carborane ceramic coating-based heat-resistant textile.
4. The carborane ceramic coating based heat resistant textile according to claim 3, wherein said 1,1 '-hydrocarbylsilylene-2, 2' -bis (dimethylsilyl) dicarboborane is 1,1 '-methylphenylsilylene-2, 2' -bis (dimethylsilyl) dicarboborane or 1,1 '-diphenylsilylene-2, 2' -bis (dimethylsilyl) dicarboborane; the metal catalyst is a palladium carbon catalyst or a platinum carbon catalyst; the ether solvent is 1, 4-dioxane, and the aromatic hydrocarbon is toluene and/or xylene; the inert atmosphere is nitrogen atmosphere; the halogenated alkane solvent is one or more of dichloromethane, dichloroethane and trichloromethane; the textile is aramid fiber textile.
5. Heat resistant textile based on carborane ceramic coatings according to claim 3,
in the step (1), the mass ratio of sodium hydroxide, water, sodium dihydrogen phosphate monohydrate, a metal catalyst and 1,1 '-hydrocarbyl silyl methylene-2, 2' -bis (dimethyl silicon base) dicarboborane is (0.2 ~ 2): (20 ~ 200): (0.2 ~ 5): (0.1 ~ 2): 0.5 ~ 5), the reaction temperature is 25 ℃ ~ 65 ℃, and the reaction time is 1 ~ 48 hours;
in the step (2), the mass ratio of the trivinyl trimethyl cyclotrisilazane to the metal catalyst to the dimethylchlorosilane is (0.5 ~ 5) to (0.001 ~ 0.2.2) to (0.5 ~ 5), the reaction temperature is 25 ℃ and ~ 85 ℃ and the reaction time is 1 ~ 48 hours;
in the step (3), the mass ratio of triethylamine to 1,1 '-alkyl silyl methylene-2, 2' -bis (dimethyl hydroxyl silyl) dicarboborane is (0.5 ~ 10) to (1 ~ 5), the reaction temperature is 25 ℃, the reaction time is ~ 75 ℃, and the reaction time is 1 ~ 48 hours;
in the step (4), the mass concentration of the carborane ceramic precursor system is 1% ~ 40%, and the mass ratio of the carborane ceramic precursor, the epoxy silane coupling agent and the diisopropadiene diepoxide is 1: 0.05: 0.1.
6. The carborane ceramic coating-based heat-resistant textile according to claim 3, wherein the carborane ceramic coating-based heat-resistant textile obtained in the step (5) is repeatedly subjected to the steps (4) and (5) to obtain the carborane ceramic coating-based heat-resistant textile.
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