Wang Yu-Cheng, Maeda Rina, Kali Gergely, Yokoyama Hideaki, Wenz Gerhard, Ito Kohzo
Material Innovation Research Center (MIRC) and Department of Advanced Materials Science, Graduate School of Frontier Sciences, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan.
Center for Chemistry and Biomedicine, Department of Pharmaceutical Chemistry, Institute of Pharmacy, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
ACS Macro Lett. 2020 Dec 15;9(12):1853-1857. doi: 10.1021/acsmacrolett.0c00648. Epub 2020 Dec 7.
A polyrotaxane (PR) with poly(methyl methacrylate) (PMMA) as the main chain polymer was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Because of the special mechanism of RAFT, the suprastructure of a PMMA-based PR is established by synthesizing inclusion complexes of methyl methacrylate and gamma-cyclodextrin (γCD) into the middle of the poly-N-(3-dimethylamino) propyl methacrylamide segments. The presence of threaded γCD was determined via diffusion ordered spectroscopy from the alignment of the mobility of γCD and the main chain polymer. A PMMA-based PR with 2-20% CD coverage and a molecular weight of 7K-60K g/mol of PMMA-based PR was synthesized with a targeted molecular structure by mediating the RAFT polymerization. The PMMA-based PR prepared in this study is expected to be suitable for wide applications of tough materials with good heat resistance. Moreover, the investigation of this synthetical approach opened possibilities for more variety of PR with controllable properties.
通过可逆加成-断裂链转移（RAFT）聚合反应制备了以聚甲基丙烯酸甲酯（PMMA）为主链聚合物的聚轮烷（PR）。由于RAFT的特殊机理，基于PMMA的PR的超结构是通过将甲基丙烯酸甲酯与γ-环糊精（γCD）的包合物合成到聚N-（3-二甲基氨基）丙基甲基丙烯酰胺链段中间而建立的。通过扩散有序光谱法，根据γCD和主链聚合物迁移率的排列确定了穿线γCD的存在。通过介导RAFT聚合反应，合成了具有2-20% CD覆盖率、分子量为7K-60K g/mol的基于PMMA的PR，并具有目标分子结构。本研究制备的基于PMMA的PR有望适用于具有良好耐热性的坚韧材料的广泛应用。此外，这种合成方法的研究为制备更多具有可控性能的PR开辟了可能性。
