Noncovalently Functionalized Poly(norbornene)s Possessing both Hydrogen Bonding and Coulombic Interactions

Abstract

Random copolymers containing both hydrogen bonding and charged ionic sites have been synthesized by the ring-opening metathesis polymerization of norbornene monomers containing either an ionic quaternary ammonium group or a 2,6-diaminopyridine functionality. All copolymers were functionalized subsequently via self-assembly using hydrogen bonding and Coulombic interactions. The hydrogen bonding interactions between 2,6-diaminopyridine and N-butylthymine were studied in the presence of the ionic quaternary ammonium group and its subsequent self-assembly with three different charged anionic species to investigate the influence of the Coulombic interactions on the strength of hydrogen bonding. It was found that hydrogen bonding was independent of the nature and presence of the Coulombic interactions. These results prove that the studied hydrogen bonding interactions are orthogonal to the Coulombic interactions and that both interactions can be used independently of each other in the same system to noncovalently functionalize polymer backbones.

DNA‐Inspired Hierarchical Polymer Design: Electrostatics and Hydrogen Bonding in Concert

“…Nair and Weck82 pioneered the combination of electrostatics and hydrogen bonding together in the same polymer backbone through the ROMP polymerization of ammonium and DAP‐functionalized norbornenes to generate a random copolymer shown in Figure 14. They investigated the influence of electrostatics and hydrogen bonding together with respect to supramolecular assembly through anion exchange and the addition of N ‐butylthymine.…”

“… “Universal Polymer Backbone” functionalized utilizing hydrogen bonding interactions and/or electrostatic interactions to synthesize new, novel polymers. Reprinted with permission82 Copyright 2006, American Chemical Society. …”

Preparation of supramolecular thermally repairable elastomer by crosslinking of maleated polyethylene‐octene elastomer with 3‐amino‐1,2,4‐triazole

“…Ionomers, ion containing polymers, show characteristic clustering of ionic aggregates (physical crosslinks) which is reversible in nature and has a profound effect on the physical and mechanical properties of the polymers . The combination of different noncovalent interactions is a convenient and efficient way for the creation of advanced or smart supramolecular architectures and the polymer properties can be precisely tailored , …”

“…13 The combination of different noncovalent interactions is a convenient and efficient way for the creation of advanced or smart supramolecular architectures and the polymer properties can be precisely tailored. 14,15 Shape memory polymers represent an important class of stimuli responsive polymers which have the capability to reversibly change from a temporary fixed shape to a permanent shape on application of a stimulus. The reverse plasticity shape memory effect, i.e.…”

Coil‐helix and sheet‐helix block copolymers via macroinitiation from telechelic ROMP polymers

“…We and others have studied the ring‐opening metathesis polymerization (ROMP) of norbornenes mediated by a ruthenium catalyst, generating telechelic poly(norbornene)s (PNBs) via functionalized Ru initiators and functionalized vinyl‐ether CTAs . Given the high modularity of ROMP and its tolerance to subsequent chain‐extensions, ROMP‐based systems have been platforms to install polymer blocks from otherwise incompatible polymerization techniques via functionalized CTAs or initiators.…”