Functional polymer particles via thiol–ene and thiol–yne suspension “click” polymerization

Abstract

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

Composite Particles From Pickering‐Stabilized Radical Mediated Thiol‐Ene Suspension Polymerizations

“…The different costabilizers used were cetyl alcohol (1‐hexadecanol), hexadecane and toluene. Concentrations of costabilizer were kept at 0.4 wt% (relative to total solution) for each reaction, while toluene was also examined at 4.15 wt% (= 50 vol% of organic species) as a comparison to our earlier work that used this amount (relative to organics) in SDS‐stabilized suspension polymerizations . Each reaction was first placed onto a minivortexer to break up the organic phase, and then sonicated using a sonic tip on the lowest power setting (for 2 min).…”

“…Previously, we and others developed radical‐mediated thiol‐ene and thiol‐yne polymerizations for the production of colloidal polymer particles . Synthesis of colloidal polymers have been shown to work in different dispersed polymerization modes, such as emulsions, dispersions, miniemulsions and suspensions .…”

Facile synthesis of functional poly(vinylene sulfide)s containing donor–acceptor chromophores by a double click reaction

“…[23][24][25][26][27][28][29] The reactions are with significant advantages that the products feature strong charge-transfer (CT) interactions in the visible absorption region, potent redox activities, and are useful for optimization of the electronic states, thereby leading to the enhanced performance of the optoelectronic devices, such as photovoltaic cells. [32][33][34][35] Moreover, the novel 36,37 In addition, as shown in Figure 1, the stretching vibration bands of ≡C-H at 3273 cm -1 and C≡C and -SH at 2556 cm -1 in the spectra of monomers became much weaker after polymerization, indicating the generation of thiol-yne click addition. [32][33][34][35] Moreover, the novel 36,37 In addition, as shown in Figure 1, the stretching vibration bands of ≡C-H at 3273 cm -1 and C≡C and -SH at 2556 cm -1 in the spectra of monomers became much weaker after polymerization, indicating the generation of thiol-yne click addition.…”

TEMPO Driven Mild and Modular Route to Functionalized Microparticles

“…Alimohammadi et al synthesized polymeric particles by thiol‐ene and thiol‐yne free radical dispersion polymerization studying the effect of initiator (photo, thermal, and redox) on the particle size. Durham et al synthesized polymeric microspheres using thiol‐ene/thiol‐yne suspension polymerization in presence of thermal and photoinitiator, while Tan et al developed porous polymer particles using water born thiol‐ene suspension polymerization and studied the effect of polymerization conditions and porogen amounts on the morphology of particles and their sizes. Jasinski et al developed poly(thioether ester) nanoparticles using a miniemulsion thiol‐ene photopolymerization approach.…”