阅读说明：本技术 一种基于碳硼烷陶瓷涂层的耐热纺织品 (Heat-resistant textile based on carborane ceramic coating ) 是由 李战雄 童德进 戴礼 王海朋 王蕾 于 2017-05-08 设计创作，主要内容包括：本发明公开了一种基于碳硼烷陶瓷涂层的耐热纺织品,包括芳纶纺织品以及碳硼烷陶瓷涂层；所述碳硼烷陶瓷由碳硼烷陶瓷前驱体制备得到；前驱体以环硅氮烷为骨架支撑,具有交联网状结构,进一步交联时有很好的陶瓷化产率,因此可在芳纶纤维表面形成致密的陶瓷涂层。提供的前驱体制备工艺简便,制备反应条件温和,原材料易得,适合工业放大化生产。经涂层处理后的芳纶纺织品耐热性能和抗氧化性能非常优异。(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.)

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.

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.