Journal
MACROMOLECULAR RAPID COMMUNICATIONS
Volume 42, Issue 18, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/marc.202000670
Keywords
cyclopolymers; cyclopolymerization; ethers; RAFT polymerization; thermoresponsive polymer s
Categories
Funding
- Japan Society for the Promotion of Science KAKENHI [JP17H03066, JP17K19159, JP19K22218, JP20H02787, JP20H05219]
- Ogasawara Foundation for the Promotion of Science Engineering
- Noguchi Institute
- Inamori Foundation
- Tokuyama Science Foundation
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Cation template-assisted RAFT cyclopolymerization can efficiently produce thermoresponsive pseudo-crown ether polymers, including large in-chain ring cyclopolymers and amphiphilic random cyclocopolymers with hydrophilic hexa(ethylene glycol) rings and hydrophobic groups.
Cation template-assisted reversible addition fragmentation/chain transfer (RAFT) cyclopolymerization of hexa(ethylene glycol) diacrylate (PEG6DA) or hexa(ethylene glycol) dimethacrylate (PEG6DMA) is developed as a versatile system to produce large in-chain ring cyclopolymers, thermoresponsive pseudo-crown ether polymers. For an efficient synthesis, potassium hexafluorophosphate (KPF6) is employed as a cation template; PEG6DA as well as PEG6DMA recognizes the potassium cation with the hexa(ethylene glycol) spacer to dynamically form a pseudo-cyclic divinyl monomer. Those monomers interacting with the potassium cations are efficiently polymerized with RAFT agents and radical initiators into cyclopolymers comprising 24-membered hexa(ethylene glycol) rings. The cation template-assisted RAFT cyclopolymerization is also effective for the synthesis of amphiphilic random cyclocopolymers bearing hydrophilic hexa(ethylene glycol) rings and hydrophobic butyl groups. Cyclopolymers of PEG6DA and PEG6DMA further show thermoresponsive solubility in water. The cloud point temperature of cyclopoly(PEG6DA)s is higher than that of a cyclopoly(PEG6DMA).
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