A new approach for modular polymer–polymer conjugations via Heck coupling

Heck coupling reactions are introduced as a modular, very efficient and highly orthogonal method for polymer–polymer conjugation. Several diblock and triblock copolymers (5200 Da ≤ Mn ≤ 17300 Da, 1.08 ≤ PDI ≤ 1.33) were prepared via Heck coupling reactions of acrylate-terminated and aryliodide-terminated polymers. The coupling reactions were performed using the so-called Jeffery's conditions, which allowed the use of equimolar amounts of reacting polymers and low reaction temperatures. Acrylated poly(ethylene glycol) monomethyl ether (PEG), poly(ε-caprolactone) (PCL) and polymers synthesized via head-to-tail selective acyclic diene metathesis (ADMET) polymerisation have been successfully conjugated with both a PEG and PCL containing an aryliodide moiety.