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Living Initiator-Transfer Anionic Polymerization of Isocyanates by Sodium Diphenylamide

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journal contribution
posted on 26.11.2019, 19:46 by Chang-Geun Chae, In-Gyu Bak, Yves Lansac, Shashadhar Samal, Yun Hee Jang, Jae-Suk Lee
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).