Model Branched Polymers: Synthesis and Characterization of Asymmetric H-Shaped Polybutadienes

A new type of model branched polymer, asymmetric H-shaped polybutadienes, consisting of central crossbars having various combinations of short and long arms attached to the ends of the crossbars, was synthesized using living anionic polymerization and chlorosilane linking chemistry. The linking agent 4-(dichloromethylsilyl)diphenylethylene provides selective reactivity to attach short or long arms on one side or both sides as desired. The samples were characterized thoroughly by size exclusion chromatography with light scattering detection (SEC-LS) and found to exhibit controlled molecular weights, as well as narrow polydispersity indices (PDIs of 1.01–1.06). Temperature gradient interaction chromatography, a method with far superior resolution as compared to SEC, also shows that these materials are well-defined, with minimal and identifiable impurities.