Ethylene-Free Synthesis of Polyethylene Copolymers and Block Copolymers

Herein, we report on a new and innovative post-polymerization modification procedure for the ethylene-free synthesis of polyethylene copolymers and block copolymers. Poly­[N-(acryloyloxy)­phthalimide] statistical and block copolymers synthesized by straightforward reversible-deactivation radical polymerization are used for thermally and photochemically induced metal-catalyzed decarboxylation yielding polyethylenes by the formation of a secondary radical at the polymer backbone that is able to react with a hydrogen source. The presented route toward various polyethylene structures via decarboxylation reactions establishes a new synthetic method in polymer chemistry, namely, the straightforward and efficient synthesis of different polyethylene block copolymers.