A novel experimental setup to measure the diffusion and the concentration of light-absorbing
molecules in particles of polymer dispersions is described. This method allows for instance quantification
of the diffusion of hydrophobic reversible addition-fragmentation chain transfer (RAFT) agents from
the monomer phase into the polymer particles during ab initio emulsion polymerization. The results
clearly show that the diffusion of the RAFT agents strongly depends on their water solubility. This explains
their influence on the kinetics of RAFT aqueous heterophase polymerization. Moreover, the retaining or
the loss of the color of the RAFT agents after addition of different initiators recorded by this method
gives direct experimental evidence that primary initiator radicals enter polymer particles.
We report here the development of a very flexible synthetic approach to generate core-shell nanoparticles below 100 nm diameter, whereby thin polymer shells are synthesized under nonaqueous conditions in a variety of organic solvents with diverse properties. This facilitates incorporation of a wide range of functional monomers and cross-linkers in the shell, without the need to make major changes to conditions or methodology. Polymer cores carrying benzyl chloride functionalities were prepared by conventional emulsion polymerization and then derivatized with sodium diethyldithiocarbamate to generate surface bound iniferters. Photoinduced second-stage surface-initiated polymerization (SIP) led to shell formation (measured as an increase in particle size by dynamic light scattering) with good control over the size distribution. The core-shell morphology of the particles generated was confirmed by transmission electron microscope (TEM) imaging and the composition of the shell layer with IR spectroscopy. The presence of ionic functionalities in the shell layer was verified by aqueous zeta potential titration studies. By exploiting the surface-initiated living radical mechanism, we have also synthesized complex multilayer particles sequentially. Even after the formation of an additional layer, the majority of the iniferter groups were re-formed as determined by elemental analysis; therefore, further particle elaboration would be possible if required.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.