Synthesis and modification of high⁃temperature hydrogen⁃containing vinyl silicone resins

doi:10.19491/j.issn.1001-9278.2025.01.006

Abstract

Abstract:

Silicone resin is a type of high⁃temperature⁃resistant material with excellent properties and exhibit broad application prospects in the field of heat resistance. With a rapid development of silicone resin for thermal protection coating in the national defense industry， it is difficult to meet the current requirement of applications. Therefore， there is a great strategic value to improve the high temperature resistance of silicone resin. Thermally stable vinyl silicone resin containing hydrogen was successfully prepared by a simple two⁃step method under acidic conditions using the alkoxysilanes containing silicon⁃hydrogen and silicon⁃ethylene bonds as raw materials. The synthesis conditions of the modified silicone resin were investigated by infrared spectroscopy and thermogravimetry analysis， and its chemical structure， thermal stability， and thermal decomposition mechanism by thermogravimetric Fourier transform infrared analysis. The results indicated that the synthesis conditions were determined to be a pH of 1.0， a hydrolysis temperature of 30 ℃， and a hydrolysis time of 3 h by using triethoxysilane and vinyl triethoxysilane as monomers and ethanol and hydrochloric acid as organic solvents. The as⁃synthesized silicone resin obtained a char yield of 97.84 % at 800 ℃ when synthesized under the optimum conditions， and its high temperature resistance was far higher than that of the ordinary silicone resin. The thermal decomposition of the hydrogen⁃containing vinyl silicone resin included two stages： the first stage occurred at about 253 ºC due to the oxidative degradation of partial vinyl of side⁃linked branches of silicone resin； The second stage taking place at 578 ºC， which was caused by the random fracture and rearrangement of SR skeletons due to the back reaction of silicone hydroxyl end groups of silicone resin.

Key words: high temperature modification, silicone resin, thermal degradation mechanism, polymer

CLC Number:

TQ324.2⁺1

HE Wenfeng, ZHAO Tongjie, XIE Yuhui, MEI Yi, XIE Delong. Synthesis and modification of high⁃temperature hydrogen⁃containing vinyl silicone resins[J]. China Plastics, 2025, 39(1): 31-36.

Figures/Tables 12

References 22

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pH值	TES含量/ mol	VTES含量/mol	H₂O含量/ mol	剩余质量/ %
1	0.03	0.03	0.195	95.58
2	0.03	0.03	0.195	94.26
3	0.03	0.03	0.195	93.54
4	0.03	0.03	0.195	93.59
5	0.03	0.03	0.195	94.08
6	0.03	0.03	0.195	93.66

pH值	TES含量/ mol	VTES含量/mol	H₂O含量/ mol	剩余质量/ %
1	0.03	0.03	0.195	95.58
2	0.03	0.03	0.195	94.26
3	0.03	0.03	0.195	93.54
4	0.03	0.03	0.195	93.59
5	0.03	0.03	0.195	94.08
6	0.03	0.03	0.195	93.66

水解温度/℃	TES 含量/mol	VTES 含量/mol	H₂O 含量/mol	pH 值	水解时间/h	剩余质量/%
30	0.03	0.03	0.195	1	3	94.11
40	0.03	0.03	0.195	1	3	95.22
50	0.03	0.03	0.195	1	3	95.58
60	0.03	0.03	0.195	1	3	96.24
70	0.03	0.03	0.195	1	3	95.72
80	0.03	0.03	0.195	1	3	96.06

水解温度/℃	TES 含量/mol	VTES 含量/mol	H₂O 含量/mol	pH 值	水解时间/h	剩余质量/%
30	0.03	0.03	0.195	1	3	94.11
40	0.03	0.03	0.195	1	3	95.22
50	0.03	0.03	0.195	1	3	95.58
60	0.03	0.03	0.195	1	3	96.24
70	0.03	0.03	0.195	1	3	95.72
80	0.03	0.03	0.195	1	3	96.06

水解时间/h	TES含量/mol	VTES含量/mol	H₂O含量/mol	pH值	水解温度/℃	水解时间/h	剩余质量/%
1	0.03	0.03	0.195	1	30	1	93.49
2	0.03	0.03	0.195	1	30	2	94.87
3	0.03	0.03	0.195	1	30	3	95.58
4	0.03	0.03	0.195	1	30	4	94.96
5	0.03	0.03	0.195	1	30	5	94.22
6	0.03	0.03	0.195	1	30	6	94.65
7	0.03	0.03	0.195	1	30	7	94.71