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9‐Borabicyclo[3.3.1]nonane (9‐BBN) initiated the polymerization of α,β‐unsaturated carbonyl monomers such as ethyl acrylate (EA) without an oxidant at low temperatures (to −90°C) under argon. Hydroquinone and 2,6‐di‐tert‐butyl‐p‐cresol had little effect on the polymerization, indicating that the propagating chain end is not a free radical. The rate of polymerization was found to be proportional to [9‐BBN]1.0 and [EA]1.5. Electron spin resonance measurements using 5,5‐dimethyl‐1‐pyrroline‐N‐oxide as a spin trap showed the absence of any radical species under polymerization conditions. No copolymerization of EA with styrene occurred. On the basis of the results obtained, this polymerization was assumed to proceed via a non‐radical mechanism.

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