Order–Disorder Transition in Supramolecular Polymers

Cortese, Jessalyn; Soulié-Ziakovic, Corinne; Cloître, Michel; Tencé‐Girault, Sylvie; Leibler, Ludwik

doi:10.1021/ja209126a

Cited by 82 publications

(127 citation statements)

References 48 publications

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“…The disordered nature of the mixture was found also in a recent investigation of the bulk system by SAXS. 22,54 From this we can safely conclude that the presented polymer RPA model delivers a good description of both the characteristic length scale (peak position) and number of supramolecularly assembling units (peak height). We emphasize that the scattering length densities were fixed to the theoretical values and only the interaction parameters between the blocks, N agg and l st needed to be optimized.…”

Section: ■ Results and Discussionsupporting

confidence: 53%

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Molecular Approach to Supramolecular Polymer Assembly by Small Angle Neutron Scattering

et al. 2013

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We present a small angle neutron scattering (SANS) study of the association of heterocomplementary telechelic polypropylene glycol (PPG) polymers, bearing either diaminotriazine (DAT) or thymine (Thy) stickers as end-groups, both in the melt and in dilute solution. The SANS data are critically examined for the architecture and morphology as well as relative extent of linear assembly in the apolar solvent toluene. A random phase approximation (RPA) approach, adapted for a supramolecularly assembled multiblock copolymer is presented, which allows to extract the interaction parameters between the constituents and the medium. From the proposed approach, which describes very well heterocomplementary hydrogen-bonding telechelic polymers in both diluted toluene solution and in the melt, we conclude that linear association prevails.

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Section: ■ Results and Discussionsupporting

confidence: 53%

“…22,54 The incompatibility between the blocks itself is somewhat larger than the empirical estimation. Although very high, they do not lead to the formation of ordered microscaled aggregation and evidence a disordered state.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Molecular Approach to Supramolecular Polymer Assembly by Small Angle Neutron Scattering

et al. 2013

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“…18,19,28,29,46,59,60 In the most simple case ( Figure 5A), the H-bond as an attractive interaction is opposed by the phase segregation acting between two different polymer chains, covalently bound to the respective H-bonds. Thus, upon mixing two different polymers (poly(A) and poly(B)) displaying inherent immiscibility but bearing specifically attracting forces on their headgroup (C and D, e.g., a specific hydrogen bonds), a wide range of structure formation can be envisioned ( Figure 5B−G).…”

Section: Clustering and Segregation: Ordering Inmentioning

confidence: 99%

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Chen

Binder

2016

Acc. Chem. Res.

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Hydrogen bonds (H-bonds) constitute highly relevant structural units of molecular self-assembly. They bridge biological and synthetic sciences, implementing dynamic properties into materials and molecules, not achieved via purely covalent bonds. Phase segregation on the other hand represents another important assembly principle, responsible for, e.g., cell compartimentation, membrane-formation, and microphase segregation in polymers. Yet, despite the expanding elegant synthetic strategies of supramolecular polymers, the investigation of phase behavior of macromolecules driven by H-bonding forces still remains in its infancy. Compared to phase segregation arising from covalently linked block copolymers, the generation of phase segregated nanostructures via supramolecular polymers facilitates the design of novel functional materials, such as those with stimuli-responsive, self-healing, and erasable-material properties. We here discuss the phase segregation of H-bonding polymers in both the solution and solid state, wherein the molecular recognition elements are based on multiple H-bonding moieties, such as thymine/2,6-diamino-pyridine (THY/DAP), thymine/diamino triazine (THY/DAT), and barbiturate/Hamilton wedge (Ba/HW) elements. The specific aggregation of a series of different H-bonding polymers in solution, both linear and dendritic polymers, bearing heterocomplementary H-bonding moieties are described, in particular focusing on the issue of phase segregation. The exploitation of H-bonded supramolecular dendrons with segregating polymer chains leads to the formation of three-phase segregated hierarchical micelles in solution, purely linking the components via H-bonds, in turn displaying a versatile spectrum of segregated morphologies. We also focus on segregation effects of H-bonded amorphous and crystalline polymers: thus the formation of nanostructures, such as disordered micelles and well-ordered body centered cubic (BCC) packed spheres from telechelic polymers bearing H-bonding moieties at the chain ends is observed. Finally, we discuss the discovery of novel functional microphase separated self-healing supramolecular architectures, illustrating dynamic and self-healing properties with an almost complete recovery of the initial mechanical performances healing within 24h at 30 °C. Collectively, our studies prove that phase segregation in H-bonding polymers is an important principle, capable to generate nanostructures and dynamic properties not achieved in covalently linked polymers. The results discussed illustrate that a rational architectural design within H-bonding polymer systems in interplay with phase segregation in both the amorphous and crystalline state opens perspectives to develop artificial supramolecular systems approaching the level of complexities and properties present in nature's biomaterials.

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“…More weakly binding supramolecular motifs on the other hand display rapid switching on account of their high sensitivity to external stimuli, but do not provide mechanical integrity unless they are supported by phase segregation phenomena . A common approach to overcome this intrinsic limitation thus relays on kinetically trapping the dynamic bonds into crystalline phases formed by the supramolecular motifs, which has been typically achieved by equipping low glass transition ( T g ) telechelic macromonomers with, e.g., hydrogen bonding end‐groups such as 4‐urazoyl benzoic acid, benzoic acid derivatives, nucleobases, urea and urethane groups, or carboxylic acid‐pyridine pairs . The assembly of such monomers and subsequent crystallization‐driven phase segregation of the supramolecular motifs produces elastomer‐like materials with mechanical properties largely dominated by the crystalline hard phase .…”

Section: Introductionmentioning

confidence: 99%

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

Sehlinger

Bartnick

Gunkel

et al. 2017

Macro Chemistry & Physics

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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.

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Order–Disorder Transition in Supramolecular Polymers

Cited by 82 publications

References 48 publications

Molecular Approach to Supramolecular Polymer Assembly by Small Angle Neutron Scattering

Molecular Approach to Supramolecular Polymer Assembly by Small Angle Neutron Scattering

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

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

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