Synthesis and Self‐Assembly of 2ndGeneration Dendritic Homopolymers and Copolymers of Polydienes with Different Isomeric Microstructures

Synthesis of 2 nd generation dendritic polymeric materials via anionic polymerization procedures in combination with chlorosilane chemistry, consisting either from one polydienic segment (homopolymers) or from two chemically different polydienic components (copolymers), is described. The polydienes used were poly(butadiene) (PB) with ∼90% 1,4-isomerism and poly(isoprene) (PI) with increased 3,4-isomerism (∼60%). Molecular characterization of intermediate products and the final dendritic materials was made with Gel Permeation Chromatography (GPC), Membrane and Vapour Pressure Osmometry (MO and VPO respectively), Gas Chromatography -Mass Spectroscopy (GC-MS) and 1 H-Nuclear Magnetic Resonance ( 1 H-NMR) Spectroscopy, leading to the conclusion that they can be considered model polymers. Morphological studies solely with Transmission Electron Microscopy (TEM) have been conducted on two of the four synthesized copolymer samples exhibiting microphase separation between the two polydiene segments.