LAMBE, UMR8587 UEVE-CNRS-CEA, Bld Fr. Mitterrand, 91000 Evry, France.
Carbohydr Polym. 2013 Apr 15;94(1):323-31. doi: 10.1016/j.carbpol.2012.12.062. Epub 2013 Jan 4.
Anionic polymerization initiated by cyclodextrins suffers from a poor solubility of those derivatives in standard polymerization solvents. The possibility to perform ethylene oxide polymerization initiated by monofunctional initiators (allyl alcohol, 2-methoxyethanol) by living ring opening polymerization in DMF, a good solvent for any CD derivative, was demonstrated by SEC, (1)H and (13)C NMR analyses. The study was extended to the use of native CD as initiator, leading to the synthesis of ill-defined structures, explained by the reactivity scale of the various hydroxyl functions. Two selectively modified CD derivatives are then used to synthesize a new family of star-shaped poly(ethylene oxide) polymers with CD core, having 14 or 21 arms. The polymerization was found to be living and DOSY experiments confirmed the well-defined structures for the synthesized star-polymers.
环糊精引发的阴离子聚合由于这些衍生物在标准聚合溶剂中的溶解度较差而受到限制。通过 SEC、（1）H 和（13）C NMR 分析，证明了在任何 CD 衍生物的良溶剂 DMF 中，通过单官能引发剂（烯丙醇、2-甲氧基乙醇）进行环氧乙烷聚合的可能性，可进行活性开环聚合。该研究扩展到使用天然 CD 作为引发剂，导致合成结构不明确，这可以用各种羟基功能的反应性尺度来解释。然后使用两种选择性修饰的 CD 衍生物合成具有 CD 核的新型星形聚（氧化乙烯）聚合物，具有 14 或 21 个臂。聚合被发现是活性的，DOSY 实验证实了合成的星形聚合物具有明确的结构。
