A photosensitive zr-b-si-c ceramic precursor and its in-situ preparation method

Abstract

The invention relates to a photosensitive Zr-B-Si-C ceramic precursor and an in-situ preparation method thereof. The method is as follows: mix methyl vinyl dichlorosilane and borane dimethyl sulfide evenly, then add metal sodium for dechlorination to obtain methyl vinyl borosilane; mix chloromethyl trichlorosilane, methyl chloride Methyldichlorosilane and dichlorozirconocene are mixed evenly, then metal magnesium is added for the first heat preservation reaction, and then a reducing agent is added for the second heat preservation reaction to obtain polyzirconium carbosilane; methylvinyl borosilane and polyzirconium Carbosilane is mixed uniformly to obtain vinyl Zr-B-Si-C alkane; vinyl Zr-B-Si-C alkane is mixed with mercaptopropionate evenly, and then a photoinitiator is added to initiate a polymerization reaction to obtain the ceramic Precursor. The invention solves the problems of high viscosity, large thermal stress, and attenuation of mechanical properties of structural parts in traditional light-curing systems, and provides high-quality raw materials for light-curing 3D printing ultra-high temperature ceramic structural parts.

Description

technical field

[0001] The invention belongs to the technical field of ceramic materials, and in particular relates to a photosensitive Zr-B-Si-C ceramic precursor and an in-situ preparation method thereof. Background technique

[0002] Based on the designability of the chemical composition of the organic polymer precursor, Zr-B-Si-C ceramic materials with specific properties can be customized according to actual application requirements. 2 A new approach to ultra-high temperature ceramic materials. At the same time, with the rapid development of 3D printing technology, this rapid net shape technology can effectively solve the problems of difficult processing of ceramic materials, long preparation cycle, and even the inability to process small and complex structural parts. Based on the particularity of ceramic printing, light curing is the preferred method for ultra-high temperature ceramic 3D printing. It is worth noting that for the precursors suitable for 3D printing of...

Examples

preparation example Construction

[0026] The present invention provides a kind of preparation method of photosensitive Zr-B-Si-C ceramic precursor in the first aspect, described method comprises the following steps:

[0027] (1) Methyl vinyl dichlorosilane (C 3 h 6 Cl 2 Si) and borane dimethyl sulfide ((CH 3 ) 2 S·BH 3 ) to mix uniformly to obtain the first mixed solution, and then add metal sodium (Na) to the first mixed solution for dechlorination to obtain methylvinyl borosilane; in the present invention, the toluene solution is, for example, toluene standard solution;

[0028] (2) Chloromethyltrichlorosilane (CH 2 Cl 4 Si), Methylchloromethyldichlorosilane (C 2 h 5 Cl 3 Si) and dichlorozirconocene (C 10 h 10 Cl 2 Zr) mix uniformly to obtain a second mixed solution, then add metal magnesium (Mg) to the second mixed solution to carry out the first heat preservation reaction to obtain a reaction solution, then add a reducing agent to the reaction solution to carry out the second heat preservation...

Embodiment 1

[0056] This embodiment provides a preparation method for in-situ synthesis of a photosensitive Zr-B-Si-C ceramic precursor, the preparation method comprising the following steps:

[0057] S1. Melt 13.4g of trimethylolpropane into 100mL of toluene solvent, add 1g of concentrated sulfuric acid as an acidic catalyst; after heating to boiling, add 31.8g of 3-mercaptopropionic acid, fully react, wash with water until neutral, and then distill under reduced pressure to obtain Mercaptopropionate.

[0058] S2, in N 2 Under the protection of an inert gas, dissolve 21.2g of methylvinyldichlorosilane into 100mL of toluene solution, then add 3.8g of borane dimethyl sulfide to obtain the first mixed solution, and then add 6.9 g of metal Na was dechlorinated, and liquid methylvinyl borosilane was obtained after standing at room temperature, extraction, and filtration.

[0059] S3, in N 2 Under inert gas protection, 18.4g (chloromethyl) trichlorosilane (CH 2 Cl 4 Si), 16.4g (chloromethy...

Embodiment 2

[0064] Embodiment 2 is basically the same as Embodiment 1, the difference is:

[0065] In step S5, the amount of benzoin dimethyl ether photoinitiator is 1 mL, that is, the amount of benzoin dimethyl ether is 0.25 wt%.

technical field

[0001] The invention belongs to the technical field of ceramic materials, and in particular relates to a photosensitive Zr-B-Si-C ceramic precursor and an in-situ preparation method thereof. Background technique

[0002] Based on the designability of the chemical composition of the organic polymer precursor, Zr-B-Si-C ceramic materials with specific properties can be customized according to actual application requirements. 2 A new approach to ultra-high temperature ceramic materials. At the same time, with the rapid development of 3D printing technology, this rapid net shape technology can effectively solve the problems of difficult processing of ceramic materials, long preparation cycle, and even the inability to process small and complex structural parts. Based on the particularity of ceramic printing, light curing is the preferred method for ultra-high temperature ceramic 3D printing. It is worth noting that for the precursors suitable for 3D printing of...

Examples

preparation example Construction

[0026] The present invention provides a kind of preparation method of photosensitive Zr-B-Si-C ceramic precursor in the first aspect, described method comprises the following steps:

[0027] (1) Methyl vinyl dichlorosilane (C 3 h 6 Cl 2 Si) and borane dimethyl sulfide ((CH 3 ) 2 S·BH 3 ) to mix uniformly to obtain the first mixed solution, and then add metal sodium (Na) to the first mixed solution for dechlorination to obtain methylvinyl borosilane; in the present invention, the toluene solution is, for example, toluene standard solution;

[0028] (2) Chloromethyltrichlorosilane (CH 2 Cl 4 Si), Methylchloromethyldichlorosilane (C 2 h 5 Cl 3 Si) and dichlorozirconocene (C 10 h 10 Cl 2 Zr) mix uniformly to obtain a second mixed solution, then add metal magnesium (Mg) to the second mixed solution to carry out the first heat preservation reaction to obtain a reaction solution, then add a reducing agent to the reaction solution to carry out the second heat preservation...

Embodiment 1

[0056] This embodiment provides a preparation method for in-situ synthesis of a photosensitive Zr-B-Si-C ceramic precursor, the preparation method comprising the following steps:

[0057] S1. Melt 13.4g of trimethylolpropane into 100mL of toluene solvent, add 1g of concentrated sulfuric acid as an acidic catalyst; after heating to boiling, add 31.8g of 3-mercaptopropionic acid, fully react, wash with water until neutral, and then distill under reduced pressure to obtain Mercaptopropionate.

[0058] S2, in N 2 Under the protection of an inert gas, dissolve 21.2g of methylvinyldichlorosilane into 100mL of toluene solution, then add 3.8g of borane dimethyl sulfide to obtain the first mixed solution, and then add 6.9 g of metal Na was dechlorinated, and liquid methylvinyl borosilane was obtained after standing at room temperature, extraction, and filtration.

[0059] S3, in N 2 Under inert gas protection, 18.4g (chloromethyl) trichlorosilane (CH 2 Cl 4 Si), 16.4g (chloromethy...

Embodiment 2

[0064] Embodiment 2 is basically the same as Embodiment 1, the difference is:

[0065] In step S5, the amount of benzoin dimethyl ether photoinitiator is 1 mL, that is, the amount of benzoin dimethyl ether is 0.25 wt%.

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