Recent developments in radical-mediated thiol-ene polymerizations include the application of these polymerizations in emulsion, dispersion, and suspension polymerizations. These step-growth polymerizations have several significant advantages over traditional chain-growth (e.g., acrylic or stryrenic) polymerizations. In particular, they allow for easy functionalization through simple stoichiometric adjustments of the monomers used in the polymerization; for example, adding a slight excess of thiol monomer produces colloidal polymer particles replete with thiol functionality. Furthermore, the subsequent use of thiol-ene (and thiol-yne) and other ‘click’ chemistries can lead to the facile production of biodegradable and bio-functionalized colloids.<br/>Our early publications showed that radical-mediated thiol-ene polymerizations can easily be performed in suspension, mini-emulsion and dispersion polymerizations. In each of these cases, the initiator is oil (monomer) soluble, and thus particles grow either from the monomer droplets (in the cases of suspension or mini-emulsion systems), or from the precipitation of the growing polymer (in dispersion polymerizations). Recently, we have shown that by using a water-soluble initiator, such as potassium persulfate (KPS), it is possible to perform thiol-ene polymerizations under conditions that essentially mimic those of traditional vinyl monomer emulsion polymerizations. Furthermore, the formation of nanoparticles that may be uniform in size is possible. Results from this study will be discussed, along with approaches to modify and functionalize these nanoparticles.

Step-growth radical thiol-ene emulsion polymerizations: Synthesis of highly functionalized nanoparticles

ACS Spring Meeting 2021

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