The Key Laboratory of Molecular Engineering of Polymer, State Education Ministry of China, Department of Macromolecular Science, Fudan University, Shanghai 200433, China.
Macromol Rapid Commun. 2011 Oct 18;32(20):1658-63. doi: 10.1002/marc.201100390. Epub 2011 Aug 19.
The eight-shaped poly(ethylene oxide) (PEO) is synthesized by a combination of Glaser coupling with ring-opening polymerization (ROP). Firstly, the star-shaped (PEO-OH)(4) is synthesized by ROP of ethylene oxide (EO) using pentaerythritol as an initiator and diphenylmethyl potassium (DPMK) as a deprotonated agent, and then the alkyne group is introduced onto the PEO arm-end to give (PEO-Alkyne)(4) in a NaH/tetrahydrofuran (THF) system. The intramolecular cyclization is carried out by a Glaser coupling reaction in a pyridine/CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) system at room temperature in an air atmosphere, and eight-shaped PEO was formed with high efficiency (almost 100%). The target polymers and intermediates were well characterized by SEC, MALDI-TOF MS, (1)H NMR and FT-IR in detail.
八臂聚氧化乙烯（PEO）通过 Glaser 偶联与开环聚合（ROP）相结合合成。首先，通过使用五甘醇作为引发剂和二苯基甲基钾（DPMK）作为脱质子试剂的环氧乙烷（EO）的 ROP 合成星形（PEO-OH）（4），然后将炔基引入 PEO 臂端，在 NaH/四氢呋喃（THF）体系中得到（PEO-炔烃）（4）。在空气气氛中的吡啶/CuBr/N，N，N'，N"，N" - 五甲基二亚乙基三胺（PMDETA）体系中，通过 Glaser 偶联反应在室温下进行分子内环化，高效地形成八臂 PEO（几乎 100%）。详细地通过 SEC、MALDI-TOF MS、（1）H NMR 和 FT-IR 对目标聚合物和中间体进行了很好的表征。
