Catalyst-Free Selective Photoactivation of RAFT Polymerization:
A Facile Route for Preparation of Comblike and Bottlebrush Polymers
Posted on 2018-09-24 - 21:43
We report a novel
photoiniferter approach toward enabling chemoselective
fragmentation of reversible addition–fragmentation chain transfer
(RAFT) polymerization using two different RAFT agents. Methyl methacrylate
(MMA) was polymerized in the presence of two different RAFT agents,
4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic
acid (CDTPA) and 2-(dodecylthiocarbonothioylthio)propionic
acid (DTPA). Both RAFT agents contain the same Z-groups but different
R-leaving groups. Under photoiniferter conditions, only one RAFT agent
was preferentially fragmented while the other remained inert. This
led to the synthesis of poly(methyl methacrylate) (PMMA) with close
correlations between theoretical and experimental molecular weights
and narrow molecular weight distributions (Mw/Mn). This approach was then employed
to homopolymerize and copolymerize a RAFT inimer, 2-(2-(n-butyltrithiocarbonate)propionate)ethyl methacrylate
(BTPEMA), under green light with CDTPA with the trithiocarbonate functionality
on the inimer incapacitated for chain transfer. Switching to blue
light irradiation allowed for photolysis of BTPEMA and grafting of
a second monomer. This novel approach provided a facile route for
the synthesis of complex macromolecular architectures such as comblike
and bottlebrush polymers without the need for intermediate steps,
such as postmodification.
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Shanmugam, Sivaprakash; Cuthbert, Julia; Kowalewski, Tomasz; Boyer, Cyrille; Matyjaszewski, Krzysztof (2018). Catalyst-Free Selective Photoactivation of RAFT Polymerization:
A Facile Route for Preparation of Comblike and Bottlebrush Polymers. ACS Publications. Collection. https://doi.org/10.1021/acs.macromol.8b01708
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AUTHORS (5)
SS
Sivaprakash Shanmugam
JC
Julia Cuthbert
TK
Tomasz Kowalewski
CB
Cyrille Boyer
KM
Krzysztof Matyjaszewski