Stable and Highly Regioselective Anionic Polymerization of (Z)-1-Phenyl[3]dendralene

The anionic polymerization of (Z)-1-phenyl[3]dendralene (1Z-P3D) in THF with potassium naphthalenide (K-Naph) as an initiator was investigated. At -78 degrees C, a polymer of predictable molecular weight and narrow molecular-weight distribution (M-w/M-n = 1.26) was obtained quantitively in 24 h. The active chain-end carbanion derived from 1Z-P3D was significantly stabilized by conjugation with a phenyl substituent at the C1 position of the monomer; side reactions such as nucleophilic addition to the double bond in other polymer main chains were not observed over a wide temperature range (-78-0 degrees C). The microstructure of the obtained poly(1Z-P3D) contained a predominant amount of the 1,4 structure (>90%). Thus, the polymerizability of 1Z-P3D was different from that of previously reported 2-phenyl[3]dendralene (P3D), in terms of the nucleophilicity of the active chain end and regioselectivity in the propagation reaction.

Automated summary

In this study, a polymer of (Z)-1-phenyl[3]dendralene was obtained through anionic polymerization with predictable molecular weight and narrow molecular-weight distribution; the polymer mainly contained a 1,4 structure (>90%); the polymerizability of 1Z-P3D was different from that of previously reported P3D.