Polyesters are a prominent class of polymer materials. The ring-opening copolymerization (ROCOP) of cyclic anhydrides and cyclic ethers has attracted attention as a method for the precise synthesis of a variety of polyesters. However, epoxides have been the primary cyclic ether employed in this method, and precise polymerization with oxetane has been challenging. This paper accomplished organobase-catalyzed ROCOP of cyclic anhydrides and oxetanes for synthesizing polyesters. By applying t-BuP₂ as a catalyst for the ROCOP of phthalic anhydride (PA) and trimethylene oxide (TO), perfectly alternating P(PA-alt-TO) was obtained with predictive molecular weights ranging from 3000 to 20,000 Da and low dispersities (Đ < 1.16). A kinetic experiment on the ROCOP of PA and TO confirmed the controlled/living nature of the proposed ROCOP system. Furthermore, its remarkable tolerance for various functional groups facilitates the utilization of a wide range of monomers and initiators, resulting in polyesters with distinct glass transition temperatures (T_g, −45.4 to 60.8 °C). Moreover, this polymerization process can be seamlessly integrated with other ROCOP processes, such as the ring-opening polymerization of trimethylene carbonate, valerolactone, or l-lactide and the ROCOP of PA/epoxide; this enables the synthesis of polyester-based block copolymers in a one-pot/one-step manner, known as self-switchable polymerization. Consequently, this novel polymerization process expands the scope of the existing ROCOP approaches and paves the way to synthesizing diverse polyesters with tailored material properties.

中文翻译：

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有机碱催化环酸酐与氧杂环丁烷开环共聚反应的建立及其在嵌段共聚物合成中的应用

聚酯是一类重要的聚合物材料。环酐和环醚的开环共聚（ROCOP）作为多种聚酯的精确合成方法而引起人们的关注。然而，环氧化物是该方法中使用的主要环醚，并且与氧杂环丁烷的精确聚合一直具有挑战性。本文完成了有机碱催化环酸酐和氧杂环丁烷的ROCOP合成聚酯。通过应用t -BuP ₂作为邻苯二甲酸酐 (PA) 和三亚甲基氧 (TO) ROCOP 的催化剂，获得了完美交替的 P(PA- alt -TO)，其预测分子量范围为 3000 至 20,000 Da，且分散度较低( Đ <1.16)。 PA 和 TO 的 ROCOP 动力学实验证实了所提出的 ROCOP 系统的受控/活动性质。此外，其对各种官能团的显着耐受性有利于多种单体和引发剂的使用，从而产生具有不同玻璃化转变温度（T _g，-45.4 至 60.8 °C）的聚酯。此外，该聚合工艺可以与其他ROCOP工艺无缝集成，例如三亚甲基碳酸酯、戊内酯或L-丙交酯的开环聚合以及PA/环氧化物的ROCOP；这使得能够以一锅/一步的方式合成聚酯基嵌段共聚物，称为自切换聚合。因此，这种新颖的聚合工艺扩展了现有 ROCOP 方法的范围，并为合成具有定制材料特性的各种聚酯铺平了道路。