Anionic homo‐ and copolymerization of double‐tailed macromonomers: A route to novel macromolecular architectures

The synthesis of model linear and star double‐comb polybutadienes, as well as molecular double‐brush polybutadienes, with two tails emanating from each branch point, is presented. The synthetic approach involves (1) the selective reaction of living polybutadienes with the two chlorines of 4‐(dichloromethylsilyl)styrene to make double‐tailed macromonomers and (2) the homopolymerization or copolymerization of the double‐tailed macromonomer, in situ without isolation, to produce the double brushes and double combs, respectively. The star double comb was synthesized by the reaction of living double‐comb polybutadiene with trichloromethylsilane. Characterization carried out by size exclusion chromatography, with differential refractometer and light scattering detectors, indicated that the synthesized polybutadienes had a high degree of molecular and structural homogeneity.