TY - JOUR
TI - Synthesis and molecular characterization of well-defined polyanion miktoarm star copolymers
AU - Pantazidis, C.
AU - Andreou, S.
AU - Nikolakakou, G.
AU - Glynos, E.
AU - Sakellariou, G.
JO - Polymer Chemistry
PY - 2022
VL - 13
TODO - 14
SP - 1997-2007
PB - Royal Society of Chemistry
SN - 1759-9954, 1759-9962
TODO - 10.1039/d2py00195k
TODO - Block copolymers;  Ethylene;  Ion exchange;  Ions;  Lithium compounds;  Lithium-ion batteries;  Living polymerization;  Macromolecules;  Molar ratio;  Network architecture, Li +;  Lithium battery applications;  Macromolecular architecture;  Miktoarm star copolymers;  Molecular characterization;  Polyanions;  Property;  Single ion;  Synthesised;  Synthetic protocols, Polyethylene oxides
TODO - Over the last year, the synthesis of polyanion copolymers has attracted considerable attention for their utilization in single-ion electrolytes in lithium battery applications. Morphology has a significant impact on the properties of such materials thus, reliable synthetic protocols are needed for different macromolecular architectures. In this work, we report the synthesis and molecular characterization of a number of novel miktoarm star copolymers consisting of poly(ethylene oxide), PEO, and poly(lithium 4-styrenesulfonyl trifluoromethylsulfonyl imide), PSTFSILi, arms and a poly(divinylbenzene), PDVB, core. Initially, a PEO-NMP macroinitiator was synthesized. The “arm-first” method, was employed to produce a PEO star with approximately 22 arms, (PEO)22, with a spacious PDVB core, bearing active NMP initiation sites. Subsequent polymerization of the STFSIK monomer (“in-out” method), followed by ion exchange using LiCl, produced well-defined PEO/PSTFSILi miktoarm stars. By varying the polymerization conditions, a series of miktoarm stars with various PSTFSILi molecular weights and Li+ molar ratios, r = [Li+]/[EO], were synthesized. A kinetic study on the polymerization of STFSIK on the PEO star core, was completed, to reveal well-controlled and “living” features. We show that the macromolecular architecture and the ratio r have a huge impact on the crystallization, the segmental dynamics, and ion-conductivity of the miktoarm star copolymers. © 2022 The Royal Society of Chemistry
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