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Living Initiator-Transfer Anionic Polymerization of Isocyanates by Sodium Diphenylamide
- Living Initiator-Transfer Anionic Polymerization of Isocyanates by Sodium Diphenylamide
- Chae, Chang-Geun; Bak, In-Gyu; Lansac, Yves; Samal, Shashadhar; Jang, Yun Hee; Lee, Jae-Suk
- DGIST Authors
- Jang, Yun Hee
- Issue Date
- Macromolecules, 52(23), 9354-9363
- Article Type
- N-HEXYL ISOCYANATE; POLY(N-HEXYL ISOCYANATE); HELICAL POLYMER; BLOCK-COPOLYMER; MACROMOLECULAR STEREOCHEMISTRY; CONFORMATIONAL CHARACTERISTICS; CHIRAL POLYISOCYANATES; LIQUID-CRYSTAL; MAIN-CHAIN; SENSE
- Access to protein-inspired polyisocyanates with high molecular weights (MWs) from anionic polymerization of isocyanates is challenging as it requires exceptional livingness. For this purpose, a dimerically self-associated sodium diphenylamide (NaDPA) was introduced as a robust chain-end-protective initiator in the anionic polymerization of n-hexyl isocyanate (HIC) in the absence or presence of sodium tetraphenylborate (NaBPh4) additive. At [NaDPA]0/[NaBPh4]0 = 5, unusual one-half initiation efficiency and one-half order of reaction kinetics were observed. Accordingly, initiator-transfer anionic polymerization (ITAP), a mechanism driven by the dimer of NaDPA ((NaDPA)2) in a dual role is proposed, in which one unimer initiates the polymerization and the other reversibly deactivates the propagating chain end through its repetitive cycles of 1:1 cross-association/dissociation. Living ITAP by NaDPA with NaBPh4 was proven by X-ray crystallography, density functional theory calculation, and quantitative yield of poly(n-hexyl isocyanate)s with an expanded range of controlled MWs (Mn = 6.09-47.8 kDa and Đ = 1.07-1.16). Copyright © 2019 American Chemical Society.
- American Chemical Society
- Related Researcher
Jang, Yun Hee
CMMM Lab(Curious Minds Molecular Modeling Laboratory)
Multiscale molecular modeling (quantum mechanics calculation; molecular dynamics simulation) : Supercomputer-assisted molecular-level understanding of materials and their chemistry; which leads to rational design of high-performance organic-inorganic-hybrid materials for clean and renewable energy as well as low-energy-consumption electronic devices
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- Department of Energy Science and EngineeringCMMM Lab(Curious Minds Molecular Modeling Laboratory)1. Journal Articles
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