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Polyethylene, PE, is a crystalline solid with a relatively high melting temperature, and it exhibits excellent solvent resistance at room temperature. In contrast, polydimethylsiloxane, PDMS, is a rubbery polymer with an ultralow glass transition temperature and poor solvent resistance. PE–PDMS block copolymers have the potential to synergistically combine these disparate properties. In spite of this potential, synthesis of PE–PDMS block copolymers has not been widely explored. We report a facile route for the synthesis of well-defined polyethylene-b-polydimethylsiloxane-b-polyethylene (EDE) triblock copolymers. Poly(1,4-butadiene)-b-polydimethylsiloxane-b-poly(1,4-butadiene) (BDB) copolymer precursors were synthesized by anionic polymerization, followed by diimide-based hydrogenation. Under the standard hydrogenation conditions established by the work of Hahn, the siloxane bond undergoes scission resulting into significant degradation of the PDMS block. Our main accomplishment is the discovery of reactio...

Synthesis of Well-Defined Polyethylene–Polydimethylsiloxane–Polyethylene Triblock Copolymers by Diimide-Based Hydrogenation of Polybutadiene Blocks