Self-switchable polymerization catalysis with monomer mixtures: using a metal-free commercial thiourea catalyst to deliver block polyesters,Polymer Chemistry

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Self-switchable polymerization catalysis with monomer mixtures: using a metal-free commercial thiourea catalyst to deliver block polyesters
Polymer Chemistry ( IF 4.1 ) Pub Date : 2023-10-10 , DOI: 10.1039/d3py00871a
Xue Liang ₁ , Wenli Wang ₁ , Dan Zhao ₁ , Hengxu Liu ₁ , Yunqing Zhu ₁

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Self-switchable polymerization is a versatile and convenient synthetic approach to producing block copolymers that utilizes different monomer mixtures and sequence polymerizations in a single pot. The development of simple and efficient metal-free organocatalysts for self-switchable polymerization is a current hot topic in research. Herein, we present a simple and cost-effective TU/PPNCl {TU: 1,3-bis[3,5-bis(trifluoromethyl)phenyl]thiourea} binary catalytic system that can switch between epoxides, cyclic anhydrides and cyclic esters, resulting in the production of sequence-controlled multiblock polyesters with a diverse range of structures. The successful construction of precise triblock copolymer structures has been confirmed through NMR, in situ IR, and SEC analysis. The experimental results confirmed the successful formation of selectively structured epoxide/anhydride and cyclic ester blocks. Metal-free thiourea catalysts show great potential for synthesizing complex polymers with sequential and structural diversity, offering opportunities for the synthesis of diverse and functional multiblock copolymer materials.

中文翻译：

单体混合物的自切换聚合催化：使用无金属的商用硫脲催化剂来提供嵌段聚酯

自转换聚合是一种通用且方便的生产嵌段共聚物的合成方法，它利用不同的单体混合物并在一个锅中进行顺序聚合。开发简单高效的用于自转换聚合的无金属有机催化剂是当前研究的热点。在此，我们提出了一种简单且经济高效的TU/PPNCl {TU: 1,3-双[3,5-双(三氟甲基)苯基]硫脲}二元催化体系，可以在环氧化物、环酸酐和环酯之间切换，产生用于生产具有多种结构的序列控制多嵌段聚酯。通过NMR、原位IR和SEC分析证实了精确三嵌段共聚物结构的成功构建。实验结果证实了选择性结构的环氧化物/酸酐和环酯嵌段的成功形成。无金属硫脲催化剂在合成具有序列和结构多样性的复杂聚合物方面显示出巨大的潜力，为合成多样化和功能性多嵌段共聚物材料提供了机会。

更新日期：2023-10-10

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