High-Yield One-Pot Synthesis of Permethylated α-Cyclodextrin-based Polyrotaxane in Hydrocarbon Solvent through an Efficient Heterogeneous Reaction
High-Yield One-Pot Synthesis of Permethylated α-Cyclodextrin-based Polyrotaxane in Hydrocarbon Solvent through an Efficient Heterogeneous Reaction
复制标题
DOI：
10.1021/ma902161d
复制
发表时间：
2010-01-26
期刊：
影响因子：
5.5
通讯作者：
Takata, Toshikazu
中科院分区：
文献类型：
--
作者：
Nakazono, Kazuko;Takashima, Tomoyuki;Takata, Toshikazu
我们实现了一个高效的一锅法合成全甲基化的α-环糊精（CD）为基础的聚轮烷通过初始络合物与胺封端的聚四氢呋喃的包合物，然后用它的大体积异氰酸酯封端在烃溶剂中在非均相条件下。在所测试的各种有机溶剂中，异辛烷是最好的溶剂，而环己烷不产生聚轮烷。详细研究了反应温度、轴聚合物的分子量、锉轮的锉结构和轴组分油对聚轮烷收率和包覆率的影响。在最佳条件下，端胺聚四氢呋喃（M-n 8700）与全甲基化α-环糊精在异辛烷中于50 ℃反应，聚轮烷的收率为71%，覆盖率为67%。我们讨论的原因和机制的有效反应发生在非均相系统中的溶剂的作用的观点和结果的无溶剂合成以前报道的。通过类似的一锅法反应，首先合成了由全甲基化α-环糊精和聚乙二醇组成的聚轮烷。当使用胺封端的聚（四氢呋喃）作为其全轴聚合物时，天然α-CD和全甲基化β-CD都没有产生任何聚轮烷。
We achieved a highly efficient one-pot synthesis of permethylated alpha-cyclodextrin(CD)-based polyrotaxane via an initial complexation to the inclusion complex with amine-terminated polytetrahydrofuran followed by end-capping with it bulky isocyanate in hydrocarbon solvent under heterogeneous conditions. Among various organic solvents tested, isooctane was the best solvent, while cyclohexane yielded no polyrotaxane. Effects of the reaction temperature, the molecular weight of the axle polymer, file structures of file wheel and axle components oil the yield and coverage ratio of the polyrotaxane were studied in detail. Under the optimum conditions, we obtained a 71% yield of polyrotaxane with it 67% coverage ratio when amine-terminated poly(tetrahydrofuran)(M-n 8700) reacted with permethylated alpha-cyclodextrin at 50 degrees C in a isooctane . We discuss the reason for and the mechanism of the efficient reaction that occurred in the heterogeneous system from the viewpoint of the role of the solvent and the results of the solvent-free synthesis previously reported. By a similar one-pot reaction, polyrotaxane consisting of permethylated alpha-cyclodextrin and poly(ethylene glycol) was first synthesized. Neither native alpha-CD nor permethylated beta-CD gave any polyrotaxanes when amine-terminated poly(tetrahydrofuran) Was used its all axle polymer.