Straightforward synthesis of poly(lauryl acrylate)-b-poly(stearyl acrylate) diblock copolymers by ATRP

Lauryl (LA) and stearyl (SA) acrylates were successfully polymerized by atom transfer radical polymerization (ATRP), leading to well defined homopolymers and diblock copolymers (PDI < 1.2). Interestingly, the polymerization was very well controlled using N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA), a ligand which had initially been reported to be unadvisable for the polymerization of such monomers. Both kinetic studies and chain extension reactions supported our conclusions. A PLA65-b-PSA47 diblock copolymer was characterized by differential scanning calorimetry and dynamic thermo-mechanical analysis, revealing that both blocks exhibit side-chain crystallinity and phase segregate in the crystalline state. The diblock behaves as a brittle rigid polymer when both blocks are crystalline, as a ductile material after the melting of the PLA phase and becomes a viscous liquid when both blocks are molten. This work could be extended to the preparation of PSA-b-PLA-b-PSA bio-issued thermoplastic elastomers.