High‐Molecular‐Weight Polycarbonates Synthesized by Enzymatic ROP of a Cyclic Carbonate as a Green Process

High‐molecular‐weight PTeMC and PHMC were prepared by the lipase‐catalyzed polymerization of butane‐1,4‐diol or hexane‐1,6‐diol and diphenyl carbonate via the formation of a cyclic dimer by a green process. Cyclic carbonate dimers were prepared by the lipase‐catalyzed condensation of diphenyl carbonate with butane‐1,4‐diol or hexane‐1,6‐diol in dilute toluene solution using an immobilized lipase from Candida antarctica , and was followed by the ring‐opening polymerization of the cyclic dimer in bulk with the same lipase to produce PTeMC with $\overline M _{\rm w}$  = 119 000 g · mol −1 and PHMC with $\overline M _{\rm w}$  = 399 000 g · mol −1 , respectively. Additionally, enzymatic polymerization of cyclic carbonate dimer was analyzed with respect to the K m and V max for the lipase.