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Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts

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Abstract

The isoselective ring-opening polymerization of racemic lactide was achieved by combining N-heterocyclic olefin (NHO) with mono(thio)ureas or bis(thio)ureas as catalytic systems. The polymerization process shows high stereoselectivity, controllability and reactivity, delivering multi-block isotactic polylactides with high chain-end fidelity and narrow molecular weight distributions. The enhancement of catalytic performance was observed in the following order: bisthiourea (DTU) < monothiourea (TU) < bisurea (DU) < urea (U). The highest Pm (probability of forming a meso dyad) = 0.91 was observed at −70 °C when using NHO/U1 catalytic system and the high stereoselectivity was attributed to chain-end control mechanism.

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Acknowledgments

This work was financially supported by the National Key R&D Plan (No. 2017YFC1104800), the National Natural Science Foundation of China (Nos. 21901249 and 21950410529), Taishan Scholars Program of Shandong Province (No. tsqn201812112), and “135” Projects Fund of CAS-QIBEBT Director Innovation Foundation and DICP & QIBEBT United Foundation (No. UN201701).

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Authors and Affiliations

  1. Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266101, China

    Zhen-Yu Wang, Guang-Qiang Xu, Li Zhou, Cheng-Dong Lv, Ru-Lin Yang, Bing-Zhe Dong & Qing-Gang Wang

  2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China

    Guang-Qiang Xu, Cheng-Dong Lv, Ru-Lin Yang, Bing-Zhe Dong & Qing-Gang Wang

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  1. Zhen-Yu Wang
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  3. Li Zhou
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Correspondence to Guang-Qiang Xu, Li Zhou or Qing-Gang Wang.

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Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts

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Wang, ZY., Xu, GQ., Zhou, L. et al. Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts. Chin J Polym Sci 39, 709–715 (2021). https://doi.org/10.1007/s10118-021-2535-x

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