A poly(vinylidene chloride-co-methyl acrylate) hybrid latex comprising CeO2 nanoparticles was successfully prepared by emulsion polymerization employing a water-soluble phosphonated macro-RAFT agent. A poly(vinylbenzylphosphonic diacid-co-styrene) statistical copolymer was first synthesized, using dibenzyl trithiocarbonate as a controlling agent, and adsorbed on ceria nanoparticles. UV-visible and 31P NMR spectroscopy proved to be efficient and complementary techniques to assess the extent of interactions between the copolymer and ceria nanoparticles, leading to a better understanding of the adsorption of phosphonated copolymer chains on inorganic particles. Then, these functionalized-CeO2 nanoparticles were used to mediate the emulsion copolymerization of vinylidene chloride and methyl acrylate in the presence of a very low amount of emulsifier. Cryo-transmission electron microscopy (cryo-TEM) confirmed the hybrid structure of the latex and the absence of either free ceria nanoparticles or free PVDC latex particles.
