Water-borne thiol-ene and thiol-yne polymer particles were synthesized using several alkene, alkyne, and thiol monomers in suspension thiol-ene and thiol-yne "click" polymerizations. In particular, we show that thiol-yne suspension polymerizations are possible, and that thermal initiation provides similar results as previously reported photoinitiation of thiol-ene monomers. The particles were analyzed in terms of particle size, glass transition temperature (T g ), and ability to undergo chemical functionalization.Composition and crosslink density clearly impacted the glass transition temperatures, with higher crosslink densities leading to higher T g values. Polymer particles with excess alkene/alkyne or thiol functionality were also synthesized to examine the influence of monomer stoichiometry on particle size and thermal properties of each system. Functionalization of thiol-ene polymer particles was demonstrated using either the inclusion of an ene-functionalized chromophore during the polymerization, or post-polymerization functionalization using thiol-isocyanate chemistry.Since monomer composition in thiol-ene and thiol-yne polymerizations can largely inuence incorporated functionality, crosslink density, and thermo-mechanical properties, we Scheme 1 General reaction mechanisms for thiol-ene and thiol-yne chemistry. Scheme 2 Structures of monomers used for (a) thiol-ene and (b) thiol-yne suspension polymerizations. (c) An example of a crosslinked polymeric network for a thiol-ene polymerization with TTT and PETMP. 66760 | RSC Adv., 2015, 5, 66757-66766 This journal is

We report the synthesis of polymeric particles using radical mediated step-growth thiolene and thiol-yne "click" dispersion polymerizations in alcoholic solvents. Various alkene, alkyne and thiol monomers were used, and thermal, photo-or redox initiation methods were all shown to be effective means to initiate polymerization. Polymer particles typically were formed with diameters in the range of several hundred nanometers, with narrow size distributions though broader than typical free-radical chain-growth dispersion polymerizations. Photoinitiation yielded the smallest sizes due to the rapid nucleation of particles as compared to redox and thermal initiation methods. Reaction kinetics were monitored by FT-IR spectroscopy for aliquot samples taken at various reaction durations. The reaction achieved full conversion in