Anionic homo- And copolymerization of styrenic triple-tailed polybutadiene macromonomers

A number of well-defined complex macromolecular architectures have been synthesized using an efficient macromonomer technique. Styrenic triple-tailed polybutadiene (PBd) macromonomers (sTMMB), synthesized by selective reaction (titration) of living PBd tails with the SiCl groups of 2-(dichloromethylsilyl) ethylchloromethylsilyl-4-styrene (TCDSS), were polymerized in situ without isolation of sTMMB with s-BuLi, using high vacuum techniques. Taking advantage of the living character of the anionic polymerization of sTMMB, the following complex macromolecular architectures were prepared: PBd-g-(PBd)₃ (triple-combs), PS-g-(PBd)₃ (triple-grafts), [PBd-#-(PBd) ₃]₃ (3-arm triple-comb stars), and triple molecular brushes (tmbPBd) or triple polymacromonomers (tPMMB). Characterization carried out by size exclusion chromatography (SEC), equipped with refractive index and light scattering detectors, indicated that the synthesized novel architectures have a high degree of molecular and compositional homogeneity.