Issue 14, 2022

Synthesis and molecular characterization of well-defined polyanion miktoarm star copolymers

Abstract

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.

Graphical abstract: Synthesis and molecular characterization of well-defined polyanion miktoarm star copolymers

Article information

Article type
Paper
Submitted
13 Feb 2022
Accepted
09 Mar 2022
First published
10 Mar 2022
This article is Open Access
Creative Commons BY license

Polym. Chem., 2022,13, 1997-2007

Synthesis and molecular characterization of well-defined polyanion miktoarm star copolymers

C. Pantazidis, S. Andreou, G. Nikolakakou, E. Glynos and G. Sakellariou, Polym. Chem., 2022, 13, 1997 DOI: 10.1039/D2PY00195K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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