Phase Segregation in Supramolecular Polymers Based on Telechelics Synthesized via Multicomponent Reactions

Abstract

The properties of supramolecular polymers in the solid state are strongly dependent on the binding strength of the supramolecular motifs used; however, It has been previously shown that the nanostructure of supramolecular polymers plays an equally important role. Supramolecular polymers are commonly synthesized via end‐group functionalization of low‐glass transition telechelics with supramolecular units. In these systems, the binding motifs segregate from the soft telechelic backbone and form a hydrogen bonded crystalline hard phase that provides physical cross‐links. To date, the reported synthetic approaches do not permit the introduction of a wide variety of supramolecular units with low synthetic effort, which would facilitate studying the structure‐property relationships. The use of the Passerini and Ugi multicomponent reactions to synthesize various poly(ethylene‐co‐butylene) telechelics with diverse amide end‐groups is reported. The thermal properties of the supramolecular polymers obtained through their solid‐state assembly are investigated and their nanophase‐segregation is studied, which is dictated by the end‐group volume fraction and the amide–amide hydrogen bonding.

Direct Catalytic Route to Biomass-Derived 2,5-Furandicarboxylic Acid and Its Use as Monomer in a Multicomponent Polymerization

“…In this respect, we investigated isocyanide-based multicomponent reactions (MCRs), among which the Passerini three-component reaction and Ugi four-component reaction (Ugi-4CR) , are particularly interesting in polymer science due to their versatility. − For instance, the direct synthesis of polyamides and polyesteramides was achieved via the Ugi reaction. More recently, isocyanide-based MCRs were used for a variety of applications in polymer science ranging from monomer synthesis − to postpolymerization modification. ,− …”

Bonding and Debonding on Demand with Temperature and Light Responsive Supramolecular Polymers

“…Therefore, the molecular weight of the PEB segment is an important parameter. For PEB telechelics, we and others have found that building blocks with an M n of 3000–8000 g mol −1 afford supramolecular polymers that exhibit thermoplastic elastomer characteristics, and their properties change from rubber‐like to viscous liquid as they are heated above the T m (Figure c) . This behavior is caused by the disassembly of the supramolecular polymers into monomeric units when the crystalline phase—which physically cross‐links the polymers and also locks the hydrogen‐bonded IPA‐Py motifs in place—melts.…”

Plasticization of a Semicrystalline Metallosupramolecular Polymer Network

“…The bulk mechanical properties and stimuli-responsive behavior of supramolecular polymers are significantly influenced by the nature of the molecular or macromolecular core that links the binding motifs and by phase separation effects, i.e., the formation of crystalline or glassy domains of the binding motifs, which act as additional physical cross-links. − There are many examples of supramolecular building blocks that contain telechelic linkers that are amorphous with a glass transition temperature ( T g ) significantly below room temperature. − The supramolecular self-assembly of such building blocks into polymers is then primarily governed by the association between the binding motifs, but such materials typically display a low stiffness and strength, similar to (thermoplastic) elastomers. When building blocks are employed that form a glassy phase with a high T g or semicrystalline domains with a high melting temperature ( T m ), the mechanical properties are often governed by the characteristics of the polymer, which can in turn hamper the association of binding motifs and the chain extension. − …”