Modified phenolic resin for fire resistive material and preparation method thereof

Abstract

The invention relates to a phenolic resin resin modified for refractories and a preparation method thereof. The technical scheme applied by the invention is that a sol-gel precursor of ferric, cobalt, or nickel metal oxide prepared by a sol-gel method are added into a dehydrated alcohol diluted phenolic resin, and the quantity of the sol-gel precursor of ferric, cobalt, or nickel metal oxide is 1-5 % by weight of the dehydrated alcohol diluted phenolic resin; the solution is stirred for 3-10 hours at the temperature of 40-85 DEG C, and then is put into a evaporator where the compound reacts for 5-10 hours at pressure of 0.08-0.09 MPa and temperature of 40-85 DEG C. Firstly, the phenolic resin modified for refractories prepared by the invention can transform the resin char from amorphous glassy carbon into crystalline graphitic carbon in-situ synthesizing a carbon nanotube in the refractories; secondly, availability of the carbon nanotube also can improve the carbon yield ratio of phenolic resin, thus improving the inoxidability, thermal shock resistance and mechanical strength for the refractories.

Description

technical field [0001] The invention belongs to the technical field of binders for composite refractory materials. In particular, it relates to a modified phenolic resin for refractory materials and a preparation method thereof. Background technique [0002] Commonly used binders for carbon composite refractory materials are asphalt and phenolic resin. Asphalt has a relatively high carbon residue rate, and there is a mesophase stage before the carbonization process, which is liquid carbonization, and the degree of graphitization of the carbonization structure is relatively high. It is in a glass state at room temperature, and the hot mixing process must be used in the mixing process with refractory granules and powders, which not only consumes energy, but also pollutes the environment due to the volatilization of a large amount of light aromatics in asphalt, especially among them. B[a]P has a strong carcinogenic effect on humans (He Junqiu, Wang Yanhua, Zhou Yanjun, etc. Th...

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Problems solved by technology

[0002] Commonly used binders for carbon composite refractory materials are asphalt and phenolic resin. Asphalt has a relatively high carbon residue rate, and there is a mesophase stage before the carbonization process, which is liquid carbonization, and the degree of graphitization of the carbonization structure is relatively high. It is in a glass state at room temperature, and the hot mixing process must be used in the mixing process with refractory granules and powders, which not only consumes energy, but also pollutes the environment due to the volatilization of a large amount of light aromatics in asphalt, especially among them. B[a]P has a strong carcinogenic effect on humans (He Junqiu, Wang Yanhua, Zhou Yanjun, etc. The current situation and improvement suggestions of carbon-containing refractory binders [J]. Fuel and Chemical Industry. 1998, 29 (1): 32~35.), which greatly affects the use of asphalt; the carbon residue rate of phenolic resin is relatively low, and it is solid carbonization, and the carbonization structure is hard graphitization carbon, but it can be adjusted to liquid, free phenol and formaldehyde content It is very low, which not only simplifies the mixing and molding process of refractory materials, but also greatly reduces environmental pollution. It is a binder widely used in Asia, Britain and the United States.

[0003] The carbonization product of phenolic resin in the heat treatment process is usually isotropic glassy carbon, which is difficult to graphitize after high temperature treatment, and there are a lot of pores in the carbonization product, so the oxidation resistance is poor

[0004] Due to the low carbon residue rate of phenolic resin, the carbonization structure is difficult to graphitize carbon (Li Nan, Zhu Boquan. Research on the carbon structure and oxidation resistance of phenolic resin [C] / / Wang Zetian, Shao Jinshun. Basic Research Papers on Refractories for Converter Steelmaking , Beijing: Metallurgical Industry Press, 1992: 246-253.), which greatly affects the high-temperature oxidation resistance, corrosion resistance, thermal shock resistance and other properties of refractory products, people hope to improve by modifying phenolic resin Its use performance in carbon composite refractory materials, however, the corresponding modification can only improve the carbon residue rate of phenolic resin to a limited extent, and has no substantial improvement on the carbonization structure