Abstract Polyaziridines (PAz) were synthesized for the first time by the 1,3-bis(isopropyl)-4,5(dimethyl)imidazol-2-ylidene-organocatalyzed ring-opening polymerization (OROP) of 2-alkyl- N - p -toluenesulfonyl aziridine (alkyl = methyl or phenyl), in the presence of both functional activated amine and non-functional non-activated amine initiators. Thus, not only an allyl-functionalized N -sulfonyl amine could serve as initiator, but also trimethylsilyl azide allowed introducing an allyl and an azido functionality in α-position of PAz chains, respectively. A non-activated and commercially available secondary amine, such as di- n -butylamine, also effectively initiated the OROP of N -tosylaziridines. Excellent control over molar masses, high chain-end fidelity and narrow dispersities ( Ð ≤ 1.20) were achieved, as attested by NMR spectroscopy, size exclusion chromatography and MALDI ToF mass spectrometry. PAz precursors consisting of the alkene or the azido functionality could further be derivatized, highlighting the accessibility of those functional groups. Overall, this N -heterocyclic carbene-OROP methodology offers a metal-free route to well-defined α-functionalized PAz.

中文翻译：

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使用功能性和非活化胺引发剂扩大 N-杂环卡宾-有机催化 N-甲苯磺酰基氮丙啶开环聚合的范围

摘要 2-烷基-N-p经1,3-双(异丙基)-4,5(二甲基)咪唑-2-亚基-有机催化开环聚合(OROP)，首次合成了聚氮丙啶(PAz)。 -甲苯磺酰基氮丙啶（烷基 = 甲基或苯基），存在功能性活化胺和非功能性非活化胺引发剂。因此，不仅烯丙基官能化的 N-磺酰胺可以作为引发剂，而且三甲基甲硅烷基叠氮化物可以分别在 PAz 链的 α 位引入烯丙基和叠氮基官能团。未活化且市售的仲胺，例如二正丁胺，也有效地引发了 N-甲苯磺酰氮丙啶的 OROP。NMR 光谱证明，实现了对摩尔质量、链端高保真度和窄分散性 (Ð ≤ 1.20) 的出色控制，体积排阻色谱和 MALDI ToF 质谱。由烯烃或叠氮基官能团组成的 PAz 前体可以进一步衍生化，突出了这些官能团的可及性。总体而言，这种 N-杂环卡宾-OROP 方法为定义明确的 α-功能化 PAz 提供了一条无金属途径。