Synthesis of Macrocyclic Poly(ethylene oxide) and Polystyrene via Glaser Coupling Reaction
Synthesis of Macrocyclic Poly(ethylene oxide) and Polystyrene via Glaser Coupling Reaction
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DOI：
10.1021/ma102330j
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发表时间：
2010-12
期刊：
影响因子：
5.5
通讯作者：
Yannan Zhang;Guowei Wang;Junlian Huang
中科院分区：
文献类型：
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作者：
Yannan Zhang;Guowei Wang;Junlian Huang
利用炔基的激光偶联反应作为一种新的闭环技术，成功地合成了单环聚环氧乙烷（PEO）和聚苯乙烯（PS）。以环氧乙烷（EO）为原料，以2,2-二甲基-1,3-丙二醇和二苯基甲基钾（DPMK）为共引发剂，端部为无水甲醇，采用开环聚合（ROP）法制备了两端有羟基的线性PEO。以萘化锂为引发剂，环氧乙烷为端部，采用阴离子聚合法制备了两端有羟基的线性聚苯乙烯。在氢化钠存在下，由羟基远旋聚合物（HO-PEO-OH和HO-PS-OH）与丙炔溴反应得到丙炔远旋前体（l-PEO和l-PS）。后者在Cu(I)Br/N，N,N ',N ',N ',N ' -五甲基二乙基三胺（PMDETA）存在下，以空气中的氧气为氧化剂，在温和条件下进行分子内环化，效率高达近100%。T…
Glaser coupling reaction of alkynyl groups was used as a new ring-closure technique to synthesize monocyclic poly(ethylene oxide) (PEO) and polystyrene (PS) successfully. The linear PEO with hydroxyl groups at both ends was prepared by ring-opening polymerization (ROP) of ethylene oxide (EO) using 2,2-dimethyl-1,3-propanediol and diphenylmethylpotassium (DPMK) as co-initiators, terminated by anhydrous methanol. The linear PS with hydroxyl groups at both ends was prepared by anionic polymerization using lithium naphthalenide as initiator and terminated by EO. The propargyl-telechelic precursors (l-PEO and l-PS) were then obtained by the reaction between hydroxyl-telechelic polymers (HO-PEO-OH and HO-PS-OH) and propargyl bromide in the presence of sodium hydride. The intramolecular cyclizations of the latter were carried out in the presence of Cu(I)Br/N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) under mild conditions with oxygen in the air as oxidant and the efficiency was as high as nearly 100%. T...