Thiol-ene and thiol-yne chemistry in microfluidics: a straightforward method towards macroporous and nonporous functional polymer beads

Abstract

Thiol-ene and thiol-yne reactions are explored as efficient pathways towards rapid production of diverse monodisperse macroporous and nonporous functional beads. In a straightforward method, polymer beads containing amine, hydroxyl and carboxyl groups have been prepared by reacting a tetrafunctional thiol with a range of mono and/or multifunctional -enes/-ynes containing the desired functional groups. The thiol-ene and thiol-yne reactions have been performed in a simple home-made microfluidic device utilizing thiol and ene/yne monomers at a 1 : 1 ratio of thiol to π-bond. The porous functional beads were prepared making use of a porogen in combination with a photoinitiator. The optical and scanning electron microscopy images demonstrated monodispersity of the beads with a spherical shape ranging in size from 210 to 600 μm. The beads were characterized in terms of glass transition temperature, surface area measurement and composition. The accessible amine and hydroxyl loading in the beads ranges from 0.23 to 0.69 mmol g⁻¹ and 0.24 to 0.64 mmol g⁻¹ respectively, as determined by the Fmoc method. This work demonstrates the applicability of thiol-ene and thiol-yne reactions in microfluidics as a powerful tool for the rapid design of functional beads for diverse applications.