Thermally vulcanized silicone rubber can be vulcanized by methods such as organic peroxides, aliphatic azo compounds, inorganic compounds and high-energy rays. The most commonly used of these are organic peroxide cure systems. Because organic peroxides are generally stable at room temperature, they can rapidly decompose at higher vulcanization temperatures (above 150°C), resulting in vulcanization. Under the initiation of organic peroxides, the organic side chain groups of the rubber undergo a vulcanization reaction to form C-C bond cross-linking. The higher the content of side chain groups such as vinyl, the easier it is to vulcanize and the higher the degree of crosslinking.

Organic peroxides for silicone rubber can be divided into two categories: general-purpose and special-purpose. The former has higher activity and can vulcanize various silicone rubbers, while the latter has lower activity and can only vulcanize vinyl-containing silicone rubber.

The vulcanizing agent BP has a fast vulcanization speed, and is often used in molded products and continuous vulcanized products, and thick-walled products are not suitable. DCBP has a low decomposition temperature and only produces low vapor pressure products during decomposition. It is especially suitable for hot air continuous vulcanization of extruded products. The rubber compound has a short storage time and is easy to scorch. The vulcanizing agents BP and DCBP are explosive, and they are commonly used as paste dispersions of silicone oil and other products (generally 50%) to facilitate safe operation and dispersion.

The vulcanizing agent DTBP is volatile (boiling point 110°C), and should be adsorbed by molecular sieves. It will not react with air or carbon black, and can be used for conductive rubber and products that are difficult to mold.

The vulcanizing agent DBPMH is very volatile at the vulcanization temperature, which can shorten the secondary vulcanization time.

Vulcanizing agent DCP is a special type for vinyl, with low volatility of decomposition products, and is suitable for vulcanization conditions with small external pressure.

Vulcanizing agent TBPB is suitable for sponge products.