CN-116120709-B - Light high-heat-resistant epoxy resin for wet winding of carbon fibers of engine housing

Abstract

The invention relates to a light high heat-resistant epoxy resin for engine shell carbon fiber wet winding, which comprises modified hollow nano silicon dioxide particles and epoxy resin, wherein the particle size of the hollow nano silicon dioxide particles is 10-30nm, and the hollow pore diameter of the modified hollow nano silicon dioxide particles is 5-20nm. According to the invention, the high-rigidity silica nanoparticles with specific size are chemically bonded with a heat-resistant epoxy system, and the scale synergistic effect of the nanoparticles can further improve the heat resistance of the epoxy resin, and particularly, according to the research of the invention, when the particle size of the silica is smaller than 10nm, a hollow structure cannot be formed, and when the particle size of the silica is 10-30nm, the silica has good dispersibility, and when the hollow pore diameter is 5-20nm, the silica has good dispersibility and good true density, so that the heat resistance of the epoxy resin can be further improved.

Inventors

• HUANG CHI
• HU MINGJIE
• LIAO JUN
• FENG XUSHENG
• ZHOU RUI
• ZHAO FEI
• ZHENG LEI

Assignees

• 湖北航泰科技有限公司
• 湖北航天技术研究院总体设计所

Dates

Publication Date

20260508

Application Date

20221202

Claims (5)

1. 1. The light high heat-resistant epoxy resin for the wet winding of the carbon fiber of the engine shell is characterized by comprising modified hollow nano silicon dioxide particles and epoxy resin, wherein the mass ratio of the modified hollow nano silicon dioxide particles to the epoxy resin is (5-20): 100, the epoxy resin is a combination of polyfunctional aromatic epoxy resin and polyfunctional epoxy diluent, the particle size of the modified hollow nano silicon dioxide particles is 10-30nm, the hollow pore diameter of the modified hollow nano silicon dioxide particles is 5-20nm, and the pore diameter and the particle size difference are not smaller than 5nm; Dispersing hollow nano silicon dioxide particles in an alcohol-water system, adding an epoxy silane coupling agent or an amino silane coupling agent at 0-100 ℃, and stirring and reacting for 1-24h; The preparation method of the hollow nano silicon dioxide particles comprises the steps of dissolving citric acid in a mixed solution of H 2 O and ethanol, adding FeCl 3 , adjusting the pH of the solution to be 9.5-10.5, adding resorcinol and formaldehyde, stirring, continuously adding absolute ethyl alcohol, ammonia water and tetraethoxysilane, stirring, centrifugally separating out products, washing with an acid solution, washing with water to remove acid, obtaining particle products, and vacuum drying the obtained particle products to obtain hollow nano silicon dioxide particles with the particle size of 10-30nm, the hollow pore diameter of 5-20nm and the pore diameter difference of not less than 5 nm.
2. 2. The light high heat-resistant epoxy resin for wet winding of carbon fibers of an engine housing according to claim 1, wherein the epoxy silane coupling agent comprises any one or a combination of more than one of epoxypropyl trimethoxysilane, epoxypropyl triethoxysilane, epoxytrimethoxysilane and epoxytriethoxysilane.
3. 3. The light high heat resistant epoxy resin for wet winding of carbon fibers of an engine housing according to claim 1, wherein the aminosilane coupling agent comprises any one or a combination of more than one of aminopropyl trimethoxysilane, aminopropyl triethoxysilane, aminoethyl trimethoxysilane, and aminoethyl triethoxysilane.
4. 4. The light high heat-resistant epoxy resin for wet winding of carbon fibers of an engine housing according to claim 1, wherein the epoxy resin is a combination of a polyfunctional aromatic epoxy resin and a polyfunctional epoxy diluent, and the polyfunctional aromatic epoxy resin comprises one or more of diglycidyl 4, 5-epoxyhexane-1, 2-diformate, trifunctional amino epoxy resin and tetraglycidyl amine type epoxy resin; The multifunctional epoxy diluent comprises one or more of ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether.
5. 5. A solid rocket motor case comprising the light highly heat-resistant epoxy resin for wet winding of carbon fibers of motor cases according to any one of claims 1 to 4.

Description

Light high-heat-resistant epoxy resin for wet winding of carbon fibers of engine housing Technical Field The invention relates to the field of solid rocket engines, in particular to a light high heat-resistant epoxy resin for wet winding of carbon fibers of an engine shell. Background In order to improve engine efficiency and reduce negative quality, large-sized solid rocket engines are generally formed by adopting a wet winding process, and the resin of the solid rocket engines is usually an epoxy resin system. However, the conventional epoxy resin system has low heat resistance, and the performance of the epoxy resin system is rapidly reduced under the aerodynamic heat in the rocket flight process, so that the overall safety of the engine is affected. The application of a curing system of the polyfunctional aromatic epoxy and the aromatic polyamine is an effective means for improving the heat resistance of the wet winding epoxy resin, and the curing system has higher heat resistance due to the fact that the system contains a large number of benzene rings with high rigidity and higher crosslinking degree. However, because the crosslinking degree of the system is higher and the density is higher, the density of the high-temperature-humidity-resistant winding resin system used in the solid rocket engine shell at present is more than 1.2g/cm 3, the negative quality of the engine is obviously increased, and the carrying capacity of the solid rocket is reduced. Disclosure of Invention The invention aims to solve the problem that the technological performance, heat resistance and low density of the existing epoxy resin for wet winding are difficult to be coordinated, and provides the light high heat resistance epoxy resin for the wet winding of the carbon fiber of the engine shell, which can simultaneously improve the heat resistance of the solid rocket engine shell and reduce the negative quality of the solid rocket engine shell, thereby improving the carrying capacity of the solid rocket engine shell. In order to achieve the technical aim, the technical scheme adopted by the invention is that the light high heat-resistant epoxy resin for the wet winding of the carbon fiber of the engine shell comprises modified hollow nano silica particles and epoxy resin, wherein the particle size of the hollow nano silica particles is 10-30nm. Further, the mass ratio of the modified hollow nano silica particles to the epoxy resin is 5-20:100. Further, the hollow pore diameter of the modified hollow nano silica particles is 5-20nm. Further, the modification method of the modified hollow nano silicon dioxide particles comprises the steps of dispersing the hollow nano silicon dioxide particles in an alcohol-water system, adding an epoxy silane coupling agent or an amino silane coupling agent at the temperature of 0-100 ℃ and stirring for reacting for 1-24h. Further, the epoxy silane coupling agent comprises any one or more than one of epoxy propyl trimethoxy silane, epoxy propyl triethoxy silane, epoxy trimethoxy silane and epoxy triethoxy silane. Further, the aminosilane coupling agent comprises any one or a combination of more than one of aminopropyl trimethoxysilane, aminopropyl triethoxysilane, aminoethyl trimethoxysilane and aminoethyl triethoxysilane. Further, the epoxy resin is a combination of a polyfunctional aromatic epoxy resin and a polyfunctional epoxy diluent, The multifunctional aromatic epoxy resin comprises one or more of 4, 5-epoxyhexane-1, 2-diglycidyl ester of dicarboxylic acid (TDE-85), trifunctional amino epoxy resin (AFG-90) and tetraglycidyl amine type epoxy resin (AG-80); The multifunctional epoxy diluent comprises one or more of ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether. Further, the preparation method of the hollow nano silicon dioxide particles comprises the steps of dissolving citric acid in a mixed solution of H 2 O and ethanol, adding FeCl 3, wherein the molar ratio of the citric acid to the FeCl 3 is 2 (1-12), adjusting the PH of the solution to 8-11, then adding resorcinol and formaldehyde, stirring, continuously adding absolute ethyl alcohol, ammonia water and ethyl orthosilicate into the system, stirring, centrifugally separating out a product, washing with an acid solution, washing with water to remove the acid, obtaining a granular product, and vacuum drying the obtained granular product to obtain the hollow nano silicon dioxide particles with the particle size of 10-30nm and the hollow pore diameter of 5-20 nm. Further, after adding FeCl 3, the pH of the solution was adjusted to 9.5-10.5. The invention also provides a solid rocket engine shell, which comprises the light high heat-resistant epoxy resin for the wet winding of the engine shell carbon fiber. Compared with the prior art, the method has the following advantages and beneficial effects: 1. according to the invention, the heat resistance of the epoxy resin can be f