Linear polymers of vinyl aryl monomers containing another unsaturated group

The synthesis and the anionic polymerization of representative substituted styrenes, CH₂?CH? C₆H₄R′, where R′ is an ethylenic or acetylenic group attached directly or indirectly to the benzene ring, to linear polymers is described. In contrast, crosslinked polymers were obtained when radical and cationic initiators were used. The unpolymerized, unsaturated bonds in R′ in the resulting linear polymers were shown to be present by infrared spectroscopic methods and by the following post-reactions of these bonds: (1) the thermal- and radical-initiated crosslinking of the linear polymers through the unsaturated bonds in R′; (2) the post-bromination of these unsaturated bonds; (3) the post-copolymerization of these unsaturated bonds with vinyl monomers; and (4) the reaction of decaborane with the acetylenic bonds. The anionic copolymerizations of methyl methacrylate, acrylonitrile, and styrene with these monomers were performed and confirmed their behavior as substituted styrenes. Block copolymerizations with styrene and methyl methacrylate were also performed and the expected results obtained. Post-bromination of the linear polymers afforded self-extinguishing polymers. The linear polymers and copolymers may be classified as “self-reactive” polymers which yield thermosetting polystyrenes.