Anionic polymerization and copolymerization of p-bromostyrene

Monodispersed poly(4-bromostyrenes) (PBs) and their block copolymers with styrene, isoprene, and 3-methylbutene were prepared and characterized by GPC and NMR. Polystyryl and α-methylstyryl carbanions act as effective initiators of the anionic polymerization of Bs in THF. The undersirable side reactions, due to thermally or photochemically induced decomposition of the bromostyryl carbanions, PBs^?, may be eliminated by conducting the reaction at ?78°C and in the dark. Under such conditions, the rate constant of propagation, k_p (?78°), is 1.5 × 10³ M^?1 s^?1. Radical anions, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Bs}^{\mathop - \limits_ \cdot} $\end{document}, formed as result of electron transfer from sodium naphthalenide to Bs, may eject spontaneously bromine ions. This step and reactions involving the respective phenyl radicals compete at ?78°C with the addition steps leading to polymer formation. Electron affinity of Bs seems to be much higher than that of styrene or isoprene, and PBs^? carbanions do not add to the latter monomers. Addition of Bs to polyisoprenyl carbanions leads to formation of the BsIBs block copolymers. BsIBs, prepared in THF, may be converted by preferential hydrogenation of the 1–2 adducts into block copolymers of Bs with poly(2-methylbutene) and isoprenyl segments. The effectiveness of Bs as a flame retarding constituent of polymeric systems seems to be much more pronounced when it is incorporated in a “block” than in a random fashion. A considerably larger fraction of PBs is required to achieve the same LOI value when the respective homopolymers are blended. Spatial distribution of the easily charred microdomains in the block copolymers is believed to be responsible for this phenomenon.