Ambient Temperature Transition-Metal-Free Dissociative Electron Transfer Reversible Addition–Fragmentation Chain Transfer Polymerization (DET-RAFT) of Methacrylates, Acrylates, and Styrene
Date
2016
Authors
Maximiano, Pedro
Mendonça, Patrícia V.
Costa, João R. C.
Haworth, Naomi
Serra, Arménio C.
Guliashvili, Tamaz
Coote, Michelle
Coelho, Jorge F. J.
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American Chemical Society
Abstract
Inorganic sulfites as reducing agents were successfully used in combination with typical reversible addition−
fragmentation chain transfer (RAFT) agents for the controlled
DET-RAFT (DET: dissociative electron transfer) of methacrylates, methyl acrylate (MA), and styrene (Sty) near room
temperature (30 °C). The polymerizations were first-order with
respect to monomer conversion and polymers with narrow
molecular weight distributions (Đ < 1.2), and “living” features
were obtained. MALDI-TOF experiments demonstrated the
integrity of the chain-ends and clearly showed the absence of
SO2 in the polymer chains. Kinetic studies revealed that an
increase of either temperature or concentration of sulfites provided faster reactions, without loss of control. Ab initio quantum
chemistry calculations suggested that in the presence of the reducing agent the RAFT agent undergoes one-electron reduction to
a stable radical anion that can then undergo fragmentation to yield the initiating carbon-centered radical. The new metal-free
DET-RAFT developed proved to be versatile and robust, as it could be also used for the polymerization of different relevant
monomers, such as glycidyl methacrylate (GMA), 2-(diisopropylamino)ethyl methacrylate (DPA), and 2-(dimethylamino)ethyl
methacrylate (DMAEMA).
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Macromolecules
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Journal article
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