Three‐ and four‐arm star shaped polymers, as well as diblock copolymers, are synthesized via acyclic diene metathesis (ADMET) polymerization. This is accomplished by using an asymmetric α,ω‐diene containing a terminal double bond and an acrylate, which is polymerized in the presence of multifunctional acrylates as selective and irreversible chain transfer agents using Hoveyda‐Grubbs second generation catalyst. High cross‐metathesis selectivities are achieved at low temperatures enabling good control over molecular weights. Furthermore, additional polyethyleneglycol (PEG) blocks are attached to these polymers via Heck coupling of the acrylate end‐groups of these polymers with aryl iodide functionalized PEG, obtaining three‐ and four‐arm star shaped di‐ and triblock copolymers with molecular weights up to 31 kDa.
