Jiang Shuangyan, Yong Zhanfu
School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China.
Qingdao Automotive Research Institute, Jilin University, Qingdao 266061, China.
Polymers (Basel). 2024 Aug 15;16(16):2304. doi: 10.3390/polym16162304.
Associating molecular structure and mechanical properties is important for silicone rubber design. Although silicone rubbers are widely used due to their odourless, non-toxic, and high- and low-temperature resistance advantages, their application and development are still limited by their poor mechanical properties. The mechanical properties of silicone rubbers can be regulated by designing the cross-link density and cross-linking structure, and altering the molar contents of vinyl in the side groups of methyl vinyl silicone rubber (MVQ) leads to different cross-linking structures and cross-linking densities in the vulcanized rubber. Therefore, this study investigated the differences in molecular parameters and molecular chain structures of unprocessed MVQ rubbers with different vinyl contents. The results showed that MVQ rubbers with high vinyl contents were branched polymers, better facilitating the cross-linking reaction than MVQ rubbers with low vinyl contents. In addition, silicone rubbers with different vinyl contents were co-cross-linked to introduce an inhomogeneous cross-linked network in the silicone rubber to improve its mechanical properties. The cross-linked network properties were analysed by the Flory-Rehner model and Mooney-Rivlin plots, and it was found that the long chains in the sparsely cross-linked domains of the network favoured high elongation at break and the short chains in the densely cross-linked domains contributed to high modulus, which could satisfy the functions of reinforcing and toughening the rubber materials at the same time. It was also found by analysing the filler network and aggregate morphology that the inhomogeneous cross-linked network led to an improvement in the dispersion of silica in the rubber and a significant improvement in the mechanical properties of silicone rubber.
关联分子结构与机械性能对于硅橡胶设计至关重要。尽管硅橡胶因其无味、无毒以及耐高低温的优势而被广泛使用,但其应用与发展仍受限于较差的机械性能。硅橡胶的机械性能可通过设计交联密度和交联结构来调节,改变甲基乙烯基硅橡胶(MVQ)侧基中乙烯基的摩尔含量会导致硫化橡胶中产生不同的交联结构和交联密度。因此,本研究考察了不同乙烯基含量的未加工MVQ橡胶在分子参数和分子链结构上的差异。结果表明,高乙烯基含量的MVQ橡胶为支化聚合物,比低乙烯基含量的MVQ橡胶更有利于交联反应。此外,将不同乙烯基含量的硅橡胶进行共交联,以在硅橡胶中引入不均匀的交联网络来改善其机械性能。通过Flory-Rehner模型和Mooney-Rivlin曲线对交联网络性能进行分析,发现网络中稀疏交联区域的长链有利于高断裂伸长率,而密集交联区域的短链有助于提高模量,这能够同时满足增强和增韧橡胶材料的功能。通过分析填料网络和聚集体形态还发现,不均匀的交联网络使二氧化硅在橡胶中的分散性得到改善,硅橡胶的机械性能显著提高。