Thiol‐epoxy “click” chemistry: Application in preparation and postpolymerization modification of polymers

Abstract

Base-catalyzed reaction between a thiol and an epoxide group is a simple fusion process that leads to the formation of a b-hydroxythio-ether linkage. This reaction is efficient, regio-selective, and fast. In addition, it produces a reactive hydroxyl group upon completion. Therefore, it is of considerable potential in synthesis of reactive and functional soft materials. Here, we discuss the fundamental aspects of this process, the so-called thiol-epoxy "click" reaction, and its utility in the preparation and post-polymerization functionaliza-tion of polymers and crosslinked networks. Furthermore, its application in surface modification of solid substrates is also considered. Finally, utility of multifunctional materials created using the thiol-epoxy reaction is discussed in the biomedical arena.

Tandem Functionalization in a Highly Branched Polymer with Layered Structure

“…[21] The two-step tandem functionalizationo fH BP(F 3 )w as carriedo ut by thiol-epoxy reaction and phenylacetylene coupling reactions (Supporting Information, Scheme S8, Figure S17). [22] Ring openingo fe poxide groups by reactionw ith thiols also generated ap endant secondary hydroxyl unit that could undergo further esterification or isocyanate-hydroxyl reaction. Similarly,e poxider ing-opening reactionw ith sodium azide in the presenceo fa mmonium chloridew as also efficient in introducing azido groups for subsequent CuAACr eaction (Supporting Information, Scheme S9 and Figure S19).…”

Preparation of Cross‐Linked Micelles from Glycidyl Methacrylate Based Block Copolymers and Their Usages as Nanoreactors in the Preparation of Gold Nanoparticles

“…SH group of AET is known to be more active to react with epoxide residues than NH 2 groups in basic pH (>11). As a result, formation of the polymer chain having SH tail group is more conceivable . In this study, it is aimed to get SH groups in micellar system by cross‐linking with AET.…”

Polyhedral oligomeric silsesquioxane-based hybrid networks obtained via thiol-epoxy click chemistry

“…Recently, thiol-epoxy reaction has been considered as click reaction since this reaction fulfills most of the click chemistry criteria including a simple catalysis, solvent-free conditions, and proceeding rapidly to high yield even at room temperature [20]. To take advantage of these features, a series of hybrid networks containing 2, 5, 10, and 15% G-POSS by weight were prepared by thiol-epoxy type click reaction using commercially available monomers, octakis-glycidyl-POSS, trimethylolpropane triglycidyl ether, and trimethylolpropane tris(3-mercaptopropionate).…”

“…Thiol-epoxy click reaction has been utilized in several applications [20] such as polymer synthesis [21,22] and functionalization [23][24][25], hydrogel [26] and high-performance coatings [27][28][29], etc. [30,31].…”