Controlled Organocatalytic Ring-Opening Polymerization of ε-Thionocaprolactone.
Controlled Organocatalytic Ring-Opening Polymerization of ε-Thionocaprolactone.
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DOI：
10.1021/acs.macromol.6b00136
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发表时间：
2016-02-09
期刊：
影响因子：
5.5
通讯作者：
Kiesewetter MK
中科院分区：
文献类型：
--
作者：
Datta PP;Kiesewetter MK
首次进行了ε-硫己内酯（tnCL）的可控开环聚合（ROP）。tnCL的有机催化ROP在没有羰基乱序的情况下发生，导致均聚（ε-硫代己内酯）（PtnCL）。通过单独的碱催化剂的ROP提出通过亲核机制进行，而H-键供体硫脲（TU）的加入被证明提供了良好的反应控制。TU提供的增加的反应控制发生在虚拟的情况下，tnCL和TU之间的结合，并讨论了这一观察的机制帐户。测量单体环应变，发现其与δ-戊内酯（VL）相似。合成了具有VL的共聚物，并且所得的共聚物材料性质的分析提供了聚（硫代（无）酯-共-酯）的唯一已知的物理表征。
For the first time, the controlled ring-opening polymerization (ROP) of ε-thionocaprolactone (tnCL) is conducted. The organocatalytic ROP of tnCL occurs without carbonyl scrambling, leading to homopoly(ε-thionocaprolactone) (PtnCL). The ROP by base catalysts alone is proposed to proceed via a nucleophilic mechanism, while the addition of an H-bond donating thiourea (TU) is shown to provide excellent reaction control. The increased reaction control provided by the TU occurs in the virtual absence of binding between tnCL and TU, and a mechanistic account for this observation is discussed. The monomer ring strain is measured and found to be similar to δ-valerolactone (VL). Copolymers with VL are synthesized, and the resulting analysis of the copolymer materials properties provides the only known physical characterizations of poly(thio(no)ester-co-ester)s.