One-Pot Synthesis of Block Copolymers Containing a Polyolefin Block

Polyolefin-containing block copolymers were catalytically synthesized using a postpolymerization modification strategy. A traditional olefin polymerization followed by a tandem hydroformylation/hydrogenation of the olefinic terminated polymer was implemented to yield a hydroxyl terminated polyolefin. The hydroxyl terminated polyolefin was then used as a macroinitiator for the ring-opening polymerization of cyclic esters to yield the corresponding diblock copolymer. This methodology was applied to an array of different polyolefins and two cyclic monomers (ϵ-caprolactone and lactide) showcasing the versatility of the protocol. Most noticeably, isotactic polypropylene was quantitatively incorporated into block copolymers. Additionally, the hydrophobicity of polyethylene films was successfully decreased by the addition of small amounts of a block copolymer.