Ebe Minami, Soga Asuka, Fujiwara Kaiyu, Ree Brian J, Marubayashi Hironori, Hagita Katsumi, Imasaki Atsushi, Baba Miru, Yamamoto Takuya, Tajima Kenji, Deguchi Tetsuo, Jinnai Hiroshi, Isono Takuya, Satoh Toshifumi
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628, Japan.
Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo, 060-8628, Japan.
Angew Chem Int Ed Engl. 2023 Aug 28;62(35):e202304493. doi: 10.1002/anie.202304493. Epub 2023 Jul 17.
Rotaxanes consisting of a high-molecular-weight axle and wheel components (macro-rotaxanes) have high structural freedom, and are attractive for soft-material applications. However, their synthesis remains underexplored. Here, we investigated macro-rotaxane formation by the topological trapping of multicyclic polydimethylsiloxanes (mc-PDMSs) in silicone networks. mc-PDMS with different numbers of cyclic units and ring sizes was synthesized by cyclopolymerization of a α,ω-norbornenyl-functionalized PDMS. Silicone networks were prepared in the presence of 10-60 wt % mc-PDMS, and the trapping efficiency of mc-PDMS was determined. In contrast to monocyclic PDMS, mc-PDMSs with more cyclic units and larger ring sizes can be quantitatively trapped in the network as macro-rotaxanes. The damping performance of a 60 wt % mc-PDMS-blended silicone network was evaluated, revealing a higher tan δ value than the bare PDMS network. Thus, macro-rotaxanes are promising as non-leaching additives for network polymers.
由高分子量轴和轮状组件组成的轮烷（大环轮烷）具有很高的结构自由度，在软材料应用中颇具吸引力。然而，其合成方法仍有待深入探索。在此，我们研究了通过多环聚二甲基硅氧烷（mc-PDMS）在硅氧烷网络中的拓扑捕获来形成大环轮烷。通过α,ω-降冰片烯基官能化的PDMS的环化聚合反应合成了具有不同环单元数量和环尺寸的mc-PDMS。在10 - 60 wt%的mc-PDMS存在下制备硅氧烷网络，并测定mc-PDMS的捕获效率。与单环PDMS不同，具有更多环单元和更大环尺寸的mc-PDMS可以作为大环轮烷定量捕获在网络中。对含60 wt% mc-PDMS的硅氧烷网络的阻尼性能进行了评估，结果表明其tan δ值高于纯PDMS网络。因此，大环轮烷有望作为网络聚合物的非渗出添加剂。
