Terpenoid-Based High-Performance Polyester with Tacticity-Independent Crystallinity and Chemical Circularity.

The development of chemically circular, bio-based polymers is an urgently needed solution to combat the plastic waste crisis. However, the most prominent, commercially implemented bio-based aliphatic polyester, poly(lactic acid) (PLA), is brittle, therefore largely limiting its broad applications. Herein, we introduce a class of aliphatic polyesters produced through the ring-opening polymerization (ROP) of (1,5S)-8,8-dimethyl-3-oxabicyclo[3.

Organocatalyzed Photoredox Radical Ring-Opening Polymerization of Functionalized Vinylcyclopropanes.

Organocatalyzed photoredox radical ring-opening polymerization (rROP) of vinylcyclopropanes (VCPs) is employed for the synthesis of polymers with controlled molecular weight (MW), dispersity, and composition. Herein, we report the study on the rROP of a variety of VCP monomers bearing diverse functional groups (such as amide, alkene, ketal, urea, hemiaminal ether, and so on) under organocatalyzed conditions with varying light sources and temperature. Notably, VCP monomers bearing natural product functionality or their derivatives can be polymerized in a controlled manner to produce poly(VCPs) with predictable MW, low dispersity, tunable composition, high thermal stability, and tailored glass transition temperature ( ), ranging 39 to 107 °C.