Synthesis of PDMAEMA–PCL–PDMAEMA triblock copolymers

The synthesis of ABA triblock copolymers of the type PDMAEMA–PCL–PDMAEMA was achieved by atom transfer radical polymerization (ATRP) of DMAEMA using difunctional polycaprolactone (PCL) as macroinitiator. First, ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) was carried out in the presence of 1,2-diaminoethane/tin (II) octanoate. Dihydroxy PCL thus obtained was end-functionalized in a quantitative manner using 2-bromoisobutyryl bromide. The resulting Br–PCL–Br was used as macroinitiator in the ATRP of DMAEMA leading to triblock copolymers with PCL as the central block and PDMAEMA sequences of different lengths. NMR and SEC analyses confirmed the formation of ABA triblocks.