Herein, we report a methodology for the synthesis of polyolefin containing block-copolymers using a catalytic postpolymerization modification strategy. The most common polyolefin grades are converted into macroinitiators using a cross-metathesis reaction. These functionalized polyolefins are then used to initiate living: coordinative ring opening polymerization of lactide, anionic ring opening polymerization of epoxide, and radical polymerization of styrene to yield the corresponding block copolymers. The high activity of the catalysts employed in the different steps offers improved practicality for scalable synthesis.
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