Block and random copolymerization of ε‐caprolactone, L‐, and rac‐lactide using titanium complex derived from aminodiol ligand

Abstract A series of di‐ and triblock copolymers [poly(L‐lactide‐b‐ε‐caprolactone), poly(D,L‐lactide‐b‐ε‐caprolactone), poly(ε‐caprolactone‐b‐L‐lactide), and poly(ε‐caprolactone‐b‐L‐lactide‐b‐ε‐caprolactone)] have been synthesized successfully by sequential ring‐opening polymerization of ε‐caprolactone (ε‐CL) and lactide (LA) either by initiating PCL block growth with living PLA chain end or vice versa using titanium complexes supported by aminodiol ligands as initiators. Poly(trimethylene carbonate‐b‐ε‐caprolactone) was also prepared. A series of random copolymers with different comonomer composition were also synthesized in solution and bulk of ε‐CL and D,L‐lactide. The chemical composition and microstructure of the copolymers suggest a random distribution with short average sequence length of both the LA and ε‐CL. Transesterification reactions played a key role in the redistribution of monomer sequence and the chain microstructures. Differential scanning calorimetry analysis of the copolymer also evidenced the random structure of the copolymer with a unique Tg. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012