Synthesis of amphiphilic poly([R,S]b-malic acid-graft-poly(e-caprolactone) graft copolymer: the 'grafting from' and 'grafting through' approaches

The synthesis of novel amphiphilic graft copolyesters based on hydrophobic poly(e-caprolactone) (PCL) segments grafted all along a hydrophilic poly((R,S)-ß-malic acid) (PMLA) backbone is proposed. These PMLA-g-PCL graft copolymers have been prepared in a controlled way using either the 'grafting through' or the 'grafting from' technique. Both approaches involve two different well-controlled ring-opening polymerization (ROP) mechanisms: anionic ROP of ß-lactones, i.e., benzyl or allyl ß-malolactonate (MLABz or MLAAllyl), and living ROP of e-caprolactone (CL) through a so-called coordination-insertion mechanism. The grafting through approach relies upon the anionic copolymerization of MLABz and ?-malolactonate-PCL macromonomer as initiated by potassium carboxylic acid salt in the presence of 1 equiv of 18-crown-6 ether. The second route follows a four-step synthesis involving the anionic ROP of MLABz and MLAAllyl, the conversion of allylic groups into pendant hydroxyl functions owing to a free-radical reaction with thioethanol in the presence of 2,2'-azobis(2-methylpropionitrile), and then the CL polymerization as initiated from these pendant -OH groups after adequate activation into aluminum alkoxide active species. Whatever the synthetic approach, the final step consists of the deprotection of the MLABz repeating units along the backbone via a soft catalytic hydrogenation reaction. The amphiphilic character of the so-prepared graft copolyesters has been evidenced by some preliminary interfacial tension experiments using the pendant drop method.