In this work, a thermal degradation mechanism of room temperature vulcanized (RTV) phenyl silicone rubber that was vulcanized by different crosslinking agents was discussed. Firstly, RTV phenyl silicone rubber samples were prepared by curing hydroxyl-terminated polymethyldiphenylsiloxane via three crosslinking agents, namely, tetraethoxysilane (TEOS), tetrapropoxysilane (TPOS), and polysilazane. Secondly, the ablation properties of RTV phenyl silicone rubber were studied by the muffle roaster test and FT-IR. Thirdly, thermal stability of the three samples was studied by thermogravimetric (TG) analysis. Finally, to explore the thermal degradation mechanism, the RTV phenyl silicone rubber vulcanized by different crosslinking agents were characterized by TG analysis-mass spectrum (TG-MS) and pyrolysis gas chromatogram-mass spectrum (pyGC-MS). Results showed that the thermal stability of RTV phenyl silicone rubber is related to the amount of residual Si–OH groups. The residual Si–OH groups initiated the polysiloxane chain degradation via an ‘unzipping’ mechanism.

Styrene-based thermoplastic elastomers (TPEs) demonstrate excellent overall performance and account for the largest industrial output. The traditional methods of preparation styrene-based thermoplastic elastomers mainly focused on anionic polymerization, and strict equipment conditions were required. In recent years, controlled/living radical polymerization (CRP) has developed rapidly, enabling the synthesis of polymers with various complex topologies while controlling their molecular weight. Herein, a series of core crosslinked star-shaped poly(styrene-b-isoprene-b-styrene)s (SISs) was synthesized for the first time via reversible addition–fragmentation chain transfer (RAFT) polymerization. Meanwhile, linear triblock SISs with a similar molecular weight were synthesized as a control. We achieved not only the controlled/living radical polymerization of isoprene but also investigated the factors influencing the star-forming process. By testing the mechanical and thermal properties and characterizing the microscopic fractional phase structure, we found that both the linear and star-shaped SISs possessed good tensile properties and a certain phase separation structure, demonstrating the characteristics of thermoplastic elastomers.