For the living ring‐opening polymerization (ROP) of epoxy monomers, the catalytic activity of organic superbases, tert‐butylimino‐tris(dimethylamino)phosphorane, 1‐tert‐butyl‐2,2,4,4,4‐pentakis(dimethylamino)‐2Λ⁵,4Λ⁵‐catenadi(phosphazene), 2,8,9‐triisobutyl‐2,5,8,9‐tetraaza‐1‐phosphabicyclo[3.3.3]undecane, and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)phosphoranylidenamino]‐2Λ⁵,4Λ⁵‐catenadi(phosphazene) (t‐Bu‐P₄), was confirmed. Among these superbases, only t‐Bu‐P₄ showed catalytic activity for the ROP of 1,2‐butylene oxide (BO) to afford poly(1,2‐butylene oxide) (PBO) with predicted molecular weight and narrow molecular weight distribution. The results of the kinetic, post‐polymerization experiments, and MALDI‐TOF MS measurement revealed that the t‐Bu‐P₄‐catalyzed ROP of BO proceeded in a living manner in which the alcohol acted as the initiator. This alcohol/t‐Bu‐P₄ system was applicable to the glycidol derivatives, such as benzyl glycidyl ether (BnGE) and t‐butyl glycidyl ether, to afford well‐defined protected polyglycidols. The α‐functionalized polyethers could be obtained using different functionalized initiators, such as 4‐vinylbenzyl alcohol, 5‐hexen‐1‐ol, and 6‐azide‐1‐hexanol. In addition, the well‐defined cyclic‐PBO and PBnGE were successfully synthesized using the combination of t‐Bu‐P₄‐catalyzed ROP and click cyclization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

中文翻译：

---

磷腈催化1,2-环氧丁烷和缩水甘油醚的开环聚合反应合成端官能化聚醚

对于环氧单体的活性开环聚合（ROP），有机超强碱，叔丁基亚氨基三（二甲基氨基）正膦，1-叔丁基-2,2,4,4,4,4-戊五（二甲基氨基）的催化活性）-2Λ ⁵，4Λ ⁵ -catena二（磷腈），2,8,9三异丁基-2,5,8,9-四氮杂-1-磷[3.3.3]十一烷，和1-叔丁基-4， 4,4-三（二甲氨基）-2,2-双[三（二甲基氨基）亚正膦-2Λ ⁵，4Λ ⁵ -catena二（磷腈）（吨-Bu-P ₄），得到了证实。在这些超级数据库中，只有t ‐Bu‐P ₄表现出对1,2-环氧丁烷（BO）ROP的催化活性，从而得到具有预测分子量和窄分子量分布的聚（1,2-环氧丁烷）（PBO）。动力学，聚合后实验和MALDI-TOF MS测量的结果表明，BO的t -Bu-P ₄催化的ROP以一种活泼的方式进行，其中醇充当了引发剂。该醇/ t -Bu-P ₄系统适用于缩水甘油衍生物，例如苄基缩水甘油醚（BnGE）和t-丁基缩水甘油醚，以提供定义明确的受保护的聚缩水甘油。α-官能化的聚醚可以使用不同的官能化引发剂获得，例如4-乙烯基苄醇，5-己烯-1-醇和6-叠氮化物-1-己醇。此外，结合使用t -Bu-P ₄催化的ROP和单击环化成功地合成了定义明确的Cycle-PBO和PBnGE 。©2012 Wiley Periodicals，Inc. J Polym Sci A部分：Polym Chem，2012年