A simple and general approach for the synthesis of biodegradable triblock copolymers by organocatalytic ROP from poly(lactide) macroinitiators

•Synthesis of biodegradable PTMC-b-PDLLA-b-PTMC and PCL-b-PDLLA-b-PCL triblock copolymers by ring opening polymerization.•General approach for biodegradable triblock copolymer synthesis with PDLLA first route with no side reactions.•Study of the catalytic influence on the block copolymerization when PDLLA is employed as macroinitiator.•Effective triblock copolymerization is obtained using cationic activated monomer mechanism.•One pot sequential copolymerization is achieved via traceless switch organocatalysis approach.