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R‑RAFT or Z‑RAFT? Well-Defined Star Block Copolymer Nano-Objects Prepared by RAFT-Mediated Polymerization-Induced Self-Assembly
journal contribution
posted on 2020-02-25, 15:50 authored by Ruiming Zeng, Ying Chen, Li Zhang, Jianbo TanReversible
addition-fragmentation chain transfer (RAFT)-mediated
polymerization-induced self-assembly (PISA) has served as a versatile
platform for the large-scale preparation of block copolymer nano-objects
with a diverse set of morphologies. However, almost all PISA formulations
are focused on the syntheses of linear block copolymers rather than
star block copolymers. Owing to the asymmetrical structure of the
RAFT agent, herein, we report a direct comparison between Z-RAFT (the
nonfragmenting group attached to the core) and R-RAFT (the fragmenting
group attached to the core) strategies for preparing well-defined
star block copolymer nano-objects via RAFT-mediated PISA. We showed
that the Z-RAFT strategy is a more suitable strategy for the preparation
of star block copolymer nano-objects without compromising the control
over the molecular weight and morphology. A binary mixture of Z-type
and R-type tetrafunctional macro-RAFT agents was used to control the
morphologies of star block copolymer assemblies. The effect of numbers
of the RAFT group on polymerization kinetics and morphologies of block
copolymer nano-objects was also investigated in detail. Finally, (ABC)4 four-arm star triblock copolymer vesicles were prepared by
seeded RAFT dispersion polymerization of solvophobic and solvophilic
monomers using (AB)4 four-arm star diblock copolymer vesicles
as seeds. This research not only expands the scope for preparing well-defined
star block copolymer nano-objects but also provides important insights
into the effect of the polymer architecture on RAFT-mediated PISA.
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Z-RAFT4 four-arm star triblock copolymer vesiclesR-type tetrafunctional macro-RAFT agentsRAFT-Mediated Polymerization-Induced Self-Assembly Reversible addition-fragmentation chain transferstar block copolymer assembliesABRAFT-mediated PISAstar block copolymers4 four-arm star diblock copolymer vesiclesmorphologieblock copolymer nano-objectsstrategyRAFT dispersion polymerizationABCR-RAFTstar block copolymer nano-objects
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