It's always a challenge to crosslink different polysiloxane oligomers through a common organic reaction to obtain high performance silicone materials. This paper reported a new type of silicone rubber (VPSR) that α,ω-aminopropyl polydimethylsiloxane (A-PDMS) was reinforced with vinyl carbonate functional polyhedral oligomeric silsesquioxane (VEC-POSS) and crosslinked by primary ammonia and cyclic carbonate reaction. VEC-POSS was synthesized from γ-mercaptopropyl polyhedral oligomeric silsesquioxane (SH-POSS) and vinyl carbonate (VEC) via the common thiol-ene click reaction. The silicones with high thermal stability, hydrophobicity and good tensile properties was obtained. FTIR confirmed the crosslinked network was formed by the combination of non-covalent bond and covalent bond. The enhancement effect of VEC-POSS was systematically studied by the experimental and molecular dynamics (MD) simulation. The results revealed that the increase of VEC-POSS contents enhanced the tensile strength and the contact angle to 3.35 MPa and 122.7°, respectively. The glass transition temperature (T_g) and the number of hydrogen bonds (H-bonds) increased with the increase of VEC-POSS contents, while the mean square displacement (MSD) and the free volume fraction (FFV) decreased gradually. Moreover, compared with the experimental results, the simulated Tg was consistent with the experimental Tan δ values, which proved the rationality of the model.

通过常见的有机反应使不同的聚硅氧烷低聚物交联以获得高效率的有机硅材料始终是一个挑战。本文报道了一种新型的硅橡胶（VPSR），其中α，ω-氨基丙基聚二甲基硅氧烷（A-PDMS）用碳酸乙烯基酯官能的多面体低聚倍半硅氧烷（VEC-POSS）增强，并通过伯氨和环状碳酸酯反应交联。VEC-POSS是由γ-巯基丙基多面体低聚倍半硅氧烷（SH-POSS）和碳酸乙烯基酯（VEC）通过常见的硫醇-烯点击反应合成的。得到具有高热稳定性，疏水性和良好的拉伸性能的有机硅。FTIR证实交联网络是由非共价键和共价键的组合形成的。通过实验和分子动力学模拟系统地研究了VEC-POSS的增强作用。结果表明，VEC-POSS含量的增加将拉伸强度和接触角分别提高到3.35 MPa和122.7°。玻璃化温度VEC-POSS含量的增加（T _g）和氢键数（H键）增加，而均方位移（MSD）和自由体积分数（FFV）逐渐降低。此外，与实验结果相比，模拟的Tg与实验的Tanδ值一致，证明了模型的合理性。