10.1021/acs.macromol.9b00940.s001
Yuna Song
Yuna
Song
Youngmu Kim
Youngmu
Kim
Yeonjin Noh
Yeonjin
Noh
Varun Kumar Singh
Varun Kumar
Singh
Santosh Kumar Behera
Santosh Kumar
Behera
Abasi Abudulimu
Abasi
Abudulimu
Kyeongwoon Chung
Kyeongwoon
Chung
Reinhold Wannemacher
Reinhold
Wannemacher
Johannes Gierschner
Johannes
Gierschner
Larry Lüer
Larry
Lüer
Min Sang Kwon
Min Sang
Kwon
Organic Photocatalyst for ppm-Level Visible-Light-Driven
Reversible Addition–Fragmentation Chain-Transfer (RAFT) Polymerization
with Excellent Oxygen Tolerance
American Chemical Society
2019
ppm-level catalyst loadings
Excellent Oxygen Tolerance
PET-RAFT
low-energy light irradiation conditions
OPC
CTA
polymerization
trithiocarbonate-based chain-transfer agent
oxygen tolerance
2019-07-17 18:35:45
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Organic_Photocatalyst_for_ppm-Level_Visible-Light-Driven_Reversible_Addition_Fragmentation_Chain-Transfer_RAFT_Polymerization_with_Excellent_Oxygen_Tolerance/8947070
A highly efficient organic photocatalyst
(OPC) for photoinduced
electron/energy-transfer reversible addition–fragmentation
chain-transfer (PET-RAFT) polymerization was identified through a
systematic catalyst design and discovery. The devised OPC offers excellent
control over PET-RAFT polymerizations of methyl methacrylate at very
low catalyst loadings (5 ppm), that is, ca. 5–50 times lower
loadings than other OPCs reported so far. Moreover, excellent oxygen
tolerance was achieved using the discovered OPC combined with trithiocarbonate-based
chain-transfer agent (CTA) under low-energy light irradiation conditions.
In depth experimental and computational investigations revealed that
(1) strong visible-light absorption and efficient generation of long-lived
triplet states of the OPC due to its unique molecular structure and
(2) the oxidation stability and no rate retardation of trithiocarbonate-based
CTA are the key to the outstanding oxygen tolerance and ppm-level
catalyst loadings. Our approach is thus believed to address a variety
of challenging tasks related to polymer synthesis and living additive
manufacturing.