Combining ATRP and ROMP with Thio‐Bromo, Copper‐Catalyzed, and Strain‐Promoted Click Reactions for Brush Copolymer Synthesis Starting from a Single Initiator/Monomer/Click Partner

Abstract

The preparation of functionalized graft copolymers utilizing a combination of ATRP, ROMP, thio‐bromo, and Huisgen‐type click chemistries is described. The construction of these polymeric architectures hinges on the use of a norbornene‐based α‐bromo ester that can act as an ATRP initiator and ROMP monomer (a so‐called inimer), as well as a thio‐bromo click partner. This allows for the use of a “grafting‐through” ROMP approach of ATRP‐based macromonomers that can undergo a post‐polymerization thio‐bromo click modification. Additionally, this material can undergo further modifications using archetypal copper‐catalyzed azide/alkyne click reaction as well as metal‐free strain‐promoted azide/alkyne click reactions.

Surface-Initiated Atom Transfer Radical Polymerization for the Preparation of Well-Defined Organic–Inorganic Hybrid Nanomaterials

“…Hybrid polymer materials are based on the covalent linkage of the polymer chain to the various inorganic substrates including nanoparticles (NPs), flat and cylindrical surfaces or the inner surface of the nanopores [30]. Such surface modification can be achieved via different techniques including (a) grafting-from [31,32,33,34,35]; (b) grafting-through [36,37,38]; (c) grafting-onto [39,40,41].…”

Postpolymerization modification of a sulfonyl fluoride‐decorated polynorbornene using the sulfur‐fluoride exchange click reaction

“…However, the foolproof nature of ROMP (thanks to the remarkable stability and functional group tolerance of Grubbs‐type initiators) allows for the efficient preparation of functional macromolecules that can easily be modified using a variety of click reactions 25–30 . For the last several years, our laboratory has also been interested in exploring the use of various click and click‐like transformations for the modification of polymers derived from ROMP 31–33 . Needless to say, we were surprised to find that there are no reports detailing the utilization of SuFEx for this purpose.…”

Post-Polymerization Modification of Ring Opening Metathesis Polymerization (ROMP)-Derived Materials Using Wittig Reactions

“…For the last few years, our laboratory [28][29][30][31][32][33] (among others [34][35][36]) has been interested in the utilization of a "thio-bromo" click [37,38] reaction for carrying out PPMs. Of particular interest to us is the modification of polymeric materials prepared from ROMP [21].…”