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Highly tunable metal-free ring opening polymerization of glycidol into various controlled topologies catalyzed by frustrated lewis pairs

Author(s)
Kim, Si EunLee, Yu-RiKim, MinseongSeo, EunyongPaik, Hyun-JongKim, Jin ChulJeong, Ji-EunPark, Young IlKim, Byeong-SuLee, Sang-Ho
Issued Date
2022-03
DOI
10.1039/d1py01442k
URI
https://scholarworks.unist.ac.kr/handle/201301/62220
Fulltext
https://pubs.rsc.org/en/content/articlelanding/2022/PY/D1PY01442K
Citation
POLYMER CHEMISTRY, v.13, no.9, pp.1243 - 1252
Abstract
Controlling the topology of a polymer is essential in determining its physical properties and processing. Even after numerous studies, obtaining a diverse array of topologies, particularly within the framework of hyperbranched systems, remains challenging. Here, we propose a synthetic approach to obtain highly tunable hyperbranched polyglycidol (hb-PG) using a frustrated Lewis pair of pyridine or tributylamine along with tris(pentafluorophenyl)borane, B(C6F5)(3), that not only influences the preferred activated monomer mechanism through hydrogen bonding with the glycidol monomer, but also facilitates the formation of unique polymer topologies. Notably, the frustrated Lewis pair containing pyridine was found to yield a branched polymer carrying cyclic structures (branched cyclic polymers) with an increased degree of branching, whereas the more sterically hindered tributylamine yielded hb-PG without a cyclic structure; these results were confirmed by MALDI-ToF analyses. Based on the unique topologies of the PGs, significant correlations between the topology and the bulk and solution states were investigated using SEC, DSC, and H-1 NMR diffusion-ordered spectroscopy.
Publisher
ROYAL SOC CHEMISTRY
ISSN
1759-9954
Keyword
HYPERBRANCHED POLYGLYCEROLSCATIONIC-POLYMERIZATIONGREEN SYNTHESISPOLYMERSDEGRADATIONPOLYETHERSMONOMERETHERARCHITECTURECOPOLYMERIZATION

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