10.1021/acs.macromol.8b02628.s001
Neomy Zaquen
Neomy
Zaquen
Ak M. N. B. P.
H. A. Kadir
Ak M. N. B. P.
H. A.
Kadir
Afiq Iasa
Afiq
Iasa
Nathaniel Corrigan
Nathaniel
Corrigan
Tanja Junkers
Tanja
Junkers
Per B. Zetterlund
Per B.
Zetterlund
Cyrille Boyer
Cyrille
Boyer
Rapid Oxygen Tolerant Aqueous RAFT Photopolymerization
in Continuous Flow Reactors
American Chemical Society
2019
di
mol
PET-RAFT
Rapid Oxygen Tolerant Aqueous RAFT Photopolymerization
Continuous Flow Reactors
PDMAA triblock copolymer
synthesis
triblock copolymers
flow reactors
reactor cascade process
2019-02-07 19:48:24
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Rapid_Oxygen_Tolerant_Aqueous_RAFT_Photopolymerization_in_Continuous_Flow_Reactors/7691927
Recently,
new controlled polymerization pathways have emerged for
the synthesis of functional polymer materials. The use of light, particularly
visible light, to generate radicals has shown to be beneficial over
thermal induction due to the high control over reaction parameters
as well as spatiotemporal control. Although numerous photopolymerizations
have been performed in batch, additional initiators or activators
are often needed to increase the overall yield, making this process
time-consuming and costly; optical path lengths directly correlate
with achievable space-time yields. The use of flow reactors is in
this case advantageous. In this work, new synthetic protocols are
demonstrated for the synthesis of di- and triblock copolymers in tubular
reactors via photoinduced electron/energy transfer-reversible addition–fragmentation
chain transfer (PET-RAFT) polymerization. Within just 10 min of polymerization
time, full monomer conversion was reached for a variety of acrylamides
and acrylates, and polymers with molecular weights up to 100000 g
mol<sup>–1</sup> and high end-group fidelity were obtained.
Changing the flow rates, concentrations, and light intensity allowed
alteration of the molecular weights, and several di- and triblock
copolymers were synthesized, indicating the high level of control
over the polymerization. In addition, multiple flow reactors were
coupled to allow the synthesis of triblock copolymers in a reactor
cascade process without the need for intermediate purification. The
attractiveness of this approach is illustrated by considering that
a PDMAA-<i>b</i>-PDMAA-<i>b</i>-PDMAA triblock
copolymer with a number-average molecular weight of 3200 g mol<sup>–1</sup> and dispersity of 1.24 could be theoretically obtained
at a rate of 300 g/day.