Enzymatic ring-opening radical polymerization

Heise, Palmans, de Geus, Villarroya and their collaborators (17,41,42) have been working on a chemoenzymatic cascade synthesis to prepare block copolymers. They combine enzymatic ring-opening polymerization (eROP) and atom transfer radical polymerization (ATRP). The synthesis of block copolymers was successful in two consecutive steps, i.e., eROP followed by ATRP. In the one-pot approach, block copolymers could be obtained by sequential addition of the ATRP catalyst, but side reactions were observed when all components were present from at the onset of reactions. A successful one-pot synthesis was achieved by conducting the reaction in supercritical carbon dioxide. 

Fig. 12 Left. One-Pot enzymatic ring opening and iiving free radical cascade polymerization [44], Right. Block copolymers by combination of enzymatic ROP and carbene-catalyzed ROP [120]...

Sha K, Li D, Li Y, Liu X, Wang S, Guan J. Synthesis, characterization, and micellization of an epoxy-based amphiphilic diblock copolymer of e-caprolactone and glycidyl methacrylate by enzymatic ring-opening polymerization and atom transfer radical polymerization. J Polym Sci, Part A Polym Chem 2007 45 5037-49. 

---