Synthesis of fatty phosphonic acid based polymethacrylamide by RAFT polymerization and self-assembly in solution

Abstract

Reversible addition–fragmentation chain-transfer (RAFT) polymerization of dimethyl(methacrylamido)dodecylphosphonate (DMADP-(OMe)₂), a new long alkyl chain methacrylamide monomer bearing phosphonated diester groups and originating from undecylenic acid, was successfully achieved in the presence of a dithioester or a trithiocarbonate chain transfer agent (CTA). Polymers with various molecular weights and low dispersities (Đ < 1.3) were obtained in a controlled way. Then, amphiphilic polymers were produced after selective hydrolysis of phosphonated diester moieties. Finally, dynamic light scattering (DLS), transmission electron microscopy (TEM) and atomic force microscopy (AFM) measurements were performed on the corresponding phosphonic diacid amphiphilic polymers showing that they were able to self-assemble in water and in organic solvent (acetonitrile), forming particles with hydrodynamic diameters of 2600 and 470 nm, respectively. By using ¹H diffusion ordered spectroscopy NMR (¹H DOSY NMR), these objects were found to possess a sharp interphase with very short mobile “hair” on their surface.