Morphology evolution of polystyrene-core/poly(N-isopropylacrylamide)-shell microgel synthesized by one-pot polymerization

One-pot polymerization with macroinitiator is supposed to be a robust,facile way to synthesize well-defined coreshell nanoparticles with fixed shell thickness.To testify this,we investigated the temperature-depending morphology evolution of polystyrene (PS) core/poly(N-isopropylacrylamide) (PNIPAM) shell microgel synthesized by one-pot polymerization with PNIPAM-RAFT as macroinitiator in dimethylformamide (DMF) by transmission electron microscopy (TEM),dynamic/static light scattering (DLS/SLS) and small angle neutron scattering (SANS).It is revealed that the microgel has a core-shell structure,i.e.,the core is made of pure PS,but the shell is composed of both PNIPAM-RAFT macroinitiator and crosslinked PS.In fact,there are 92.0 wt％ D2O,6.7 wt％ PNIPAM and 1.3 wt％ PS in the shell in its aqueous dispersion at 21 ℃;therefore,its shell thickness is much larger than the extended chain length of the macroinitiator as revealed by both SANS and DLS observations.Competitive growth of styrene,divinylbenzene and PNIPAM macroinitiator as well as possible chain transfer from amine proton of PNIPAM side chain may lead to the larger shell thickness,compared with the extended chain length of the macroinitiator.Our work can shed light on the real morphology control in one-pot polymerization.