Synthesis of eight-shaped poly(ethylene oxide) by the combination of Glaser coupling with ring-opening polymerization.
Synthesis of eight-shaped poly(ethylene oxide) by the combination of Glaser coupling with ring-opening polymerization.
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DOI：
10.1002/marc.201100390
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发表时间：
2011-10
影响因子：
4.6
通讯作者：
Guowei Wang;Xiaoshan Fan;Bin Hu;Yannan Zhang;Junlian Huang
中科院分区：
文献类型：
--
作者：
Guowei Wang;Xiaoshan Fan;Bin Hu;Yannan Zhang;Junlian Huang
采用激光偶联和开环聚合相结合的方法合成了八字形聚氧乙烷(PEO)。首先，在NaH/四氢呋喃(THF)体系中，以季戊四醇为引发剂，环氧乙烷(EO)为原料，二苯基甲基钾(DPMK)为去质子剂，由环氧乙烷(EO)经ROP反应合成星形(PEO-OH)(4)，然后在PEO臂末端引入炔基得到(PEO-Alkyne)(4)。在室温空气气氛中，在吡啶/溴化铜/N，N，N‘，N“，N”-五甲基二亚乙三胺(PMDETA)体系中，分子内环化反应通过Gaser偶联反应进行，得到了高效率(近100%)的八字形PEO。目标聚合物和中间体通过SEC、MALDI-TOF MS、(1)HNMR和FT-IR进行了详细的表征。
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.