
Organocatalyzed Photoredox Radical Ring-Opening Polymerization of Functionalized Vinylcyclopropanes
Author(s) -
Dian-Feng Chen,
Simone Bernsten,
Garret M. Miyake
Publication year - 2020
Publication title -
macromolecules
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.994
H-Index - 313
eISSN - 1520-5835
pISSN - 0024-9297
DOI - 10.1021/acs.macromol.0c01367
Subject(s) - dispersity , polymer chemistry , polymerization , monomer , chemistry , radical polymerization , polymer , ring opening polymerization , organic chemistry
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 °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.