Journal
MACROMOLECULES
Volume 53, Issue 19, Pages 8352-8359Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.0c01367
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- Colorado State University
- National Institute of General Medical Sciences of the National Institutes of Health [R35GM119702]
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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 (T-g), ranging 39 to 107 degrees C. Lastly, successful grafting through synthesis of molecular brush copolymers containing 1.0 or 5.0 kDa polydimethylsiloxane (PDMS) side chains from readily accessible EtVCP-PDMS macromonomers further demonstrates the robustness of this organocatalyzed photoredox rROP.
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