Jung Philipp, Ziegler Arthur D, Blankenburg Jan, Frey Holger
Institut für organische Chemie, Johannes-Gutenberg Universität Mainz, Duesbergweg 10-14, 55099, Mainz, Germany.
Graduate School Materials Science in Mainz, 55128, Mainz, Germany.
Angew Chem Int Ed Engl. 2019 Sep 9;58(37):12883-12886. doi: 10.1002/anie.201904203. Epub 2019 Aug 19.
Glycidyl tosylate appears to be a non-polymerizable epoxide when nucleophilic initiators are used because of the excellent leaving group properties of the tosylate. However, using the monomer-activated mechanism, this unusual monomer can be copolymerized with ethylene oxide (EO) and propylene oxide (PO), respectively, yielding copolymers with 7-25 % incorporated tosylate-moieties. The microstructure of the copolymers was investigated via in situ H NMR spectroscopy, and the reactivity ratios of the copolymerizations have been determined. Quantitative nucleophilic substitution of the tosylate-moiety is demonstrated for several examples. This new structure provides access to a library of functionalized polyethers that cannot be synthesized by conventional oxyanionic polymerization.
由于对甲苯磺酸酯具有出色的离去基团性质，当使用亲核引发剂时，对甲苯磺酸缩水甘油酯似乎是一种不可聚合的环氧化物。然而，采用单体活化机制，这种特殊的单体可以分别与环氧乙烷（EO）和环氧丙烷（PO）共聚，得到含有7 - 25%对甲苯磺酸酯基团的共聚物。通过原位核磁共振氢谱对共聚物的微观结构进行了研究，并确定了共聚反应的竞聚率。通过几个实例证明了对甲苯磺酸酯基团的定量亲核取代。这种新结构为一系列功能化聚醚提供了合成途径，而这些聚醚是无法通过传统的氧阴离子聚合合成的。
