A step-wise self-assembly approach in preparation of multi-responsive poly(styrene-co-methyl methacrylate) nanoparticles containing spiropyran.

HYPOTHESIS: Surfactant-free emulsion polymerization has become favorable due to circumventing instability issues reasonably. Incorporation of an appropriate hydrophilic macroRAFT, could provide controlled in-situ self-assembly via copolymerization with hydrophobic monomers into polymer particles. So far, this approach has mostly been studied in dispersion systems and further studies are needed in emulsions. Beside the corresponding mechanistic studies, the prepared latex particles would potentially exhibit smart behaviors by choosing stimuli-responsive monomers.

EXPERIMENTS: Poly(styrene-co-methyl methacrylate) latexes were prepared by utilizing pH-responsive polydimethylaminoethyl methacrylate as the hydrophilic segment through polymerization induced self-assembly (PISA). A systematic study on the effect of MMA amount, role of smart spiropyran ethylacrylate (SPEA) comonomer and the synthesized macroRAFT for inducing efficient assembly has been performed comparatively for the first time.

FINDINGS: SEM and DLS analyses showed the effect of MMA content on the obtaining of spherical particles with bimodal or monodisperse size distributions in both series of samples. Kinetic studies through conversion measurements along with GPC analysis revealed that the incorporation of MMA and SPEA strongly affected the efficiency of in-situ self-assembly, particle formation and RAFT-controllability on molecular weights. Ultimately, acido/basochromism, pH-responsivity and UV-responsivity of the prepared latexes were verified and the results showed their facile and fast multi-responsivity.