Spherical, individual polymer nanoparticles with functional -SH groups were synthesized via aerosol photopolymerization (APP) employing radically initiated thiol-ene chemistry. A series of various thiol and alkene monomer combinations were investigated based on di-, tri-, and tetrafunctional thiols with difunctional allyl and vinyl ethers, and di- and trifunctional acrylates. Only thiol and alkene monomer combinations able to build cross-linked poly(thio-ether) networks were compatible with APP, which requires fast polymerization of the generated droplet aerosol during the photoreactor passage within a residence time of half-minute. Higher monomer functionalities and equal overall stoichiometry of functional groups resulted in the best nanoparticles being spherical and individual, proven by scanning electron microscopy (SEM). The presence of reactive -SH groups in the synthesized nanoparticles as a basis for post-polymerization modifications was verified by Ellman's test.
Keywords: aerosol photopolymerization; polymer nanoparticles; thiol-ene polymerization; thiol-functional nanoparticles.