阅读说明：本技术 Poss功能化的氧化铝陶瓷前驱体及其制备方法 (POSS functionalized alumina ceramic precursor and preparation method thereof ) 是由 马小民 张春苏 李富萍 陈卫东 张迎锋 吴南春 于 2020-05-20 设计创作，主要内容包括：本发明公开了一种POSS功能化的氧化铝陶瓷前驱体及其制备方法。该复合前驱体的制备方法包括：将带有功能基团的POSS单体与铝源在有机溶液中混合,加入一定量的催化剂,搅拌反应一定时间后,除去有机溶剂即可制备得到POSS功能化的氧化铝陶瓷前驱体。该氧化铝陶瓷前驱体可与多种有机溶剂互溶得到氧化铝陶瓷前驱体溶液,通过前驱体质量分数的调节可控制溶液的黏度在100-1000mpa·s,可用浸渍法制备POSS增强氧化铝陶瓷纤维,也可通过溶胶-凝胶转变制备POSS增强的氧化铝陶瓷纤维,克服了传统方法工艺性差的缺点,有利于获得耐高温连续陶瓷长纤维。(The invention discloses a POSS functionalized alumina ceramic precursor and a preparation method thereof. The preparation method of the composite precursor comprises the following steps: the POSS monomer with functional groups and an aluminum source are mixed in an organic solution, a certain amount of catalyst is added, after stirring and reacting for a certain time, the organic solvent is removed, and the POSS functionalized alumina ceramic precursor can be prepared. The alumina ceramic precursor can be mutually dissolved with various organic solvents to obtain an alumina ceramic precursor solution, the viscosity of the solution can be controlled to be at 100-MPa & s by adjusting the mass fraction of the precursor, POSS reinforced alumina ceramic fibers can be prepared by an impregnation method, and POSS reinforced alumina ceramic fibers can also be prepared by sol-gel conversion, so that the defect of poor manufacturability of the traditional method is overcome, and the high-temperature resistant continuous ceramic long fibers can be obtained.)

1. A preparation method of a POSS functionalized alumina ceramic precursor is characterized by comprising the following steps:

(1) POSS and an aluminum source are mixed in an organic solution;

(2) adding a certain amount of catalyst, and stirring for reacting for a certain time;

(3) and removing the organic solvent to prepare the POSS functionalized alumina ceramic precursor.

2. The method for preparing a POSS-functionalized alumina ceramic precursor as claimed in claim 1, wherein in step (1), the POSS comprises any one or a combination of two or more of amino POSS, vinyl POSS, phenyl POSS, ethoxy POSS, methoxy POSS, or a composite POSS of the above functional groups.

3. The method for preparing a POSS functionalized alumina ceramic precursor as claimed in claim 1, wherein in step (1), the aluminum source comprises any one or a combination of two or more of aluminum powder, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum silicate, aluminum sulfide, aluminum isopropoxide and aluminum nitrate nonahydrate.

4. The method for preparing a POSS functionalized alumina ceramic precursor as claimed in claim 1, wherein in step (1), the organic solvent comprises any one or a combination of two or more of methanol, ethanol, isopropanol, propanol, butanol, tert-butanol, N-hexane, tetrahydrofuran, N-methylpyrrolidone, acetone, dimethyl sulfoxide, and N, N-dimethylformamide.

5. The method for preparing the POSS functionalized alumina ceramic precursor as claimed in claim 1, wherein in the step (1), the mass ratio of POSS to the aluminum source is 1: 10-1: 100; and/or the dosage of the solvent is 2-5 times of the total mass of the POSS and the aluminum source.

6. The method for preparing a POSS functionalized alumina ceramic precursor as claimed in claim 1, wherein in step (2), the catalyst comprises any one or a combination of two or more of sodium hydroxide, potassium hydroxide, urea, ammonia water, pyridine, trimethylammonium chloride, and triethylamine; and/or the amount of the catalyst is less than 1% of the POSS mass fraction.

7. The method of preparing a POSS functionalized alumina ceramic precursor as claimed in claim 1 wherein the reaction temperature of step (2) is from room temperature to 80 ℃.

8. The method for preparing a POSS functionalized alumina ceramic precursor as claimed in claim 1, wherein in the step (2), the reaction time is 3-10 hours.

9. The method for preparing a POSS functionalized alumina ceramic precursor as claimed in claim 1, wherein the organic solvent removal method in step (3) comprises reduced pressure drying, spray drying, freeze drying, rotary evaporation drying.

10. A POSS functionalized alumina ceramic precursor obtained from the method of preparing a POSS functionalized alumina ceramic precursor according to any of claims 1 to 9, wherein the alumina ceramic precursor consists of POSS and an aluminum source.

Technical Field

The invention belongs to the field of ceramic precursors, and particularly relates to a POSS modified alumina ceramic precursor and a preparation method thereof.

Background

POSS is cage-type polysilsesquioxane, is a novel organic matter and hybrid compound, and has excellent anti-atomic oxidation performance. POSS molecular size is 1-3 nanometers, and the POSS can be divided into polyfunctional group POSS and monofunctional group POSS according to the number of active functional groups. Structurally, the POSS is a cage-shaped inner shell formed by an Si-O alternating framework, and can inhibit the molecular chain movement of a composite component to endow the hybrid material with excellent thermal stability, mechanical property and flame retardance. On the other hand, the POSS has small size, small size effect, quantum size effect and macroscopic quantum tunneling effect, and external active groups can react with various groups, so that the POSS is favorably and uniformly distributed and stable in the hybrid material. POSS is therefore widely used for the functional modification of polymeric and inorganic materials.

Ceramics refer to a class of inorganic non-metallic materials made from natural or synthetic compounds through processes such as forming, high temperature sintering, etc. Has the advantages of high melting point, high hardness, high wear resistance, oxidation resistance and the like. In addition, ceramic materials have unique mechanical, thermal, electrical, chemical and optical properties. As typical representative materials of structural ceramics, ceramics based on alumina, silicon nitride, and silicon carbide have excellent high temperature resistance, and are widely used in components working at high temperatures, such as rocket nozzle tips, thermocouple tubes, furnace tubes, and the like, heat exchanger materials at high temperatures, and grinding wheels, abrasives, and the like manufactured with high hardness and wear resistance. In order to further realize the regulation and optimization of the structural ceramic performance, researchers make a large number of researches on the relationship between the ceramic structure and the performance, and develop the relationship between the internal microstructure (microcrystal face effect and porous multiphase distribution condition) and the mechanical performance, the relationship between the ceramic material performance (such as light, electricity, heat and magnetism) and the forming, the particle size distribution and the adhesive interface. The POSS structure is introduced into the preparation of the ceramic, so that the synergistic effect is hopeful to be realized, the ceramic functionalization and mechanical enhancement are realized, the thermal stability is improved, and the like.

Disclosure of Invention

Aiming at the defects of the prior art and the limitation of materials, the invention mainly aims to provide a POSS functionalized alumina ceramic precursor and a preparation method thereof.

The gain effect of the invention is as follows: (1) POSS has excellent stability and reactivity, can form stable chemical bonds with alumina to achieve the aim of modification, so that the prepared composite alumina ceramic has good solubility, and the sol-gel spinning preparation of alumina ceramic fibers is facilitated. (2) Because POSS and alumina are chemically bonded, after the ceramic is formed by sintering, a uniform and stable silica shell layer is formed on the periphery of an alumina crystal region, and the thermal stability and the high temperature resistance of the alumina ceramic are improved.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the invention provides high-temperature-resistant ceramic precursor slurry and a preparation method thereof, wherein the preparation method comprises the following three key steps:

(1) POSS and an aluminum source are mixed in an organic solution;

(2) adding a certain amount of catalyst, and stirring for reacting for a certain time;

(3) and removing the organic solvent to prepare the POSS functionalized alumina ceramic precursor.

As one of preferable modes, the POSS includes any one or a combination of two or more of amino POSS, vinyl POSS, phenyl POSS, ethoxy POSS, methoxy POSS, or composite POSS of the above functional groups, and is not limited thereto.

Further, the aluminum source includes any one or a combination of two or more of aluminum powder, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum silicate, aluminum sulfide, aluminum isopropoxide, and aluminum nitrate nonahydrate, and is not limited thereto.

Further, the solvent includes methanol, ethanol, isopropanol, propanol, butanol, t-butanol, N-hexane, tetrahydrofuran, N-methylpyrrolidone, acetone, dimethyl sulfoxide, N-dimethylformamide, and is not limited thereto.

Further, the mass ratio of the POSS to the aluminum source is 1: 10-1: 100.

Furthermore, the dosage of the solvent is 2-5 times of the total mass of the POSS and the aluminum source.

As one of preferable embodiments, the catalyst includes any one or a combination of two or more of sodium hydroxide, potassium hydroxide, urea, ammonia water, pyridine, trimethylammonium chloride, and triethylamine, and is not limited thereto.

Further, the amount of the catalyst is less than 1% of the mass fraction of POSS.

Further, the reaction temperature is room temperature to 80 ℃.

Further, the reaction time is 3-10 hours.

As a preferable mode, the method for removing the organic solvent includes reduced pressure drying, spray drying, freeze drying, rotary evaporation drying.

Drawings

FIG. 1 is a schematic structural view of POSS functionalized alumina ceramic precursors obtained in examples 1-6 of the present invention;

FIG. 2 is a scanning electron micrograph of a POSS functionalized alumina ceramic precursor obtained in example 1 of the present invention;

FIG. 3 is a scanning electron microscope image of a POSS functionalized alumina ceramic precursor obtained in example 2 of the present invention;

FIG. 4 is a scanning electron micrograph of a POSS functionalized alumina ceramic precursor obtained in example 3 of the present invention;

FIG. 5 is a scanning electron micrograph of a POSS functionalized alumina ceramic precursor obtained in example 4 of the present invention;

FIG. 6 is a scanning electron micrograph of a POSS functionalized alumina ceramic precursor obtained in example 5 of the present invention;

FIG. 7 is a scanning electron micrograph of POSS functionalized alumina ceramic precursor obtained in example 6 of the present invention.

Detailed Description

In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. Firstly, a POSS functionalized alumina ceramic precursor and a preparation method thereof are provided.

One aspect of an embodiment of the present invention provides a method for preparing a POSS functionalized alumina ceramic precursor, comprising three key steps:

(1) POSS and an aluminum source are mixed in an organic solution;

(2) adding a certain amount of catalyst, and stirring for reacting for a certain time;

(3) and removing the organic solvent to prepare the POSS functionalized alumina ceramic precursor.

In some embodiments, the POSS includes any one or combination of two or more of amino POSS, vinyl POSS, phenyl POSS, ethoxy POSS, methoxy POSS, or complex POSS of the above functional groups, without limitation thereto.

Further, the aluminum source includes any one or a combination of two or more of aluminum powder, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum silicate, aluminum sulfide, aluminum isopropoxide, and aluminum nitrate nonahydrate, and is not limited thereto.

Further, the solvent includes methanol, ethanol, isopropanol, propanol, butanol, t-butanol, N-hexane, tetrahydrofuran, N-methylpyrrolidone, acetone, dimethyl sulfoxide, N-dimethylformamide, and is not limited thereto.

Further, the mass ratio of the POSS to the aluminum source is 1: 10-1: 100.

Furthermore, the dosage of the solvent is 2-5 times of the total mass of the POSS and the aluminum source.

In some embodiments, the catalyst includes any one or a combination of two or more of sodium hydroxide, potassium hydroxide, urea, ammonia, pyridine, trimethylammonium chloride, and triethylamine, and is not limited thereto.

Further, the amount of the catalyst is less than 1% of the mass fraction of POSS.

Further, the reaction temperature is room temperature to 80 ℃.

Further, the reaction time is 3-10 hours.

In some embodiments, the organic solvent removal process comprises reduced pressure drying, spray drying, freeze drying, rotary evaporation drying.

The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.