Aqueous one-pot synthesis of epoxy-functional diblock copolymer worms from a single monomer: new anisotropic scaffolds for potential charge storage applications
Nitroxide-functional polymers have garnered
considerable interest in recent years and appear to hold promise for energy
storage applications. However, their synthesis can be both expensive and
time-consuming. Here, we propose a highly convenient method for the preparation
of TEMPO-functional diblock copolymer nanoparticles directly in water.
Epoxy-functional diblock copolymer worms are synthesized from a single monomer,
glycidyl methacrylate (GlyMA), using a three-step, one-pot protocol in aqueous
solution via polymerization-induced self-assembly (PISA). First, an initial
aqueous emulsion of GlyMA was heated at 85 °C for 9 h to afford an aqueous
solution of glycerol monomethacrylate (GMA). Then reversible
addition-fragmentation chain transfer (RAFT) polymerization of GMA was
conducted in aqueous solution using a dicarboxylic acid-based RAFT agent to
produce a water-soluble PGMA homopolymer. Finally, chain extension of this
pre-cursor block via RAFT aqueous emulsion polymerization of GlyMA at 50 °C produced
amphiphilic diblock copolymer chains that self-assembled in situ to form a 15%
w/w aqueous dispersion of diblock copolymer worms. These worms can be
derivatized directly using 4-amino-TEMPO in aqueous solution, affording novel
crosslinked anisotropic nanoparticles that contain a relatively high density of
stable nitroxide radicals for potential charge storage applications
Funding
EPSRC for a Particle Technology Fellowship grant (EP/R003009/1)
ERC Advanced Investigator grant (PISA 320372)
U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award DE-SC0014336
U.S. National Institute of Health under award number P41GM103521
History
School
- Aeronautical, Automotive, Chemical and Materials Engineering
Department
- Materials
Published in
Polymer ChemistryVolume
10Issue
2Pages
194 - 200Publisher
Royal Society of Chemistry (RSC)Version
- AM (Accepted Manuscript)
Rights holder
© Royal Society of ChemistryPublisher statement
This paper was accepted for publication in the journal Polymer Chemistry and the definitive published version is available at https://doi.org/10.1039/c8py01427bAcceptance date
2018-11-14Publication date
2018-11-29Copyright date
2019ISSN
1759-9954eISSN
1759-9962Publisher version
Language
- en