Supramolecular association of acid-terminated polydimethylsiloxanes. IV. NMR investigation of hydrogen bonding interactions and apparent molecular weight in the bulk state

Duweltz, D.; Lauprêtre, F.; Abed, S.; Bouteiller, Laurent; Boileau, Sylvie

doi:10.1016/s0032-3861(03)00058-2

Cited by 11 publications

(4 citation statements)

References 15 publications

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“…An alternative approach is to use phase segregation in conjunction with supramolecular motifs that have small binding constants. Thus, polymer-like properties may be attainable with low molecular weight compounds in which a soft core segment has weakly interacting hard segments attached at both ends (Figure a). − If phase segregation occurs, the effective molarity of the chain ends would be greatly increased, thus enhancing their degree of interaction. Additionally, the presence of supramolecular interactions may aid phase segregation.…”

Section: Supramolecular Polymers and Phase Segregationmentioning

confidence: 99%

Supramolecular Polymerizations and Main-Chain Supramolecular Polymers

2009

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The past few decades have seen a significant growth in the field of supramolecular polymerizations, in which (reversible) noncovalent interactions (e.g., hydrogen bonding, metal-ligand coordination, π-π stacking, etc.) between (macro)monomeric units are utilized to build polymeric assemblies. These polymeric aggregates can exist in an equilibrium state between low and high molecular weight species, which in turn opens the door to a new matrix of properties. For example, such supramolecular polymers are potentially an interesting class of stimuli-or environmentally responsive, "smart" materials. Additionally, the establishment of an equilibrium during the assembly process imparts on the system the ability to "proofread" assemblies and, depending on the nature of the (macro)molecules, can allow efficient access to controlled, well-defined nanostructures. This Perspective will focus on the basic concepts of such supramolecular polymerizations, such as mechanism of assembly growth, and the effects of growth kinetics, phase segregation, and growth on the surface has on the assembly and properties of the resulting supramolecular polymers, highlighting these concepts with selected literature examples.

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Section: Supramolecular Polymers and Phase Segregationmentioning

confidence: 99%

Supramolecular Polymerizations and Main-Chain Supramolecular Polymers

2009

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“…There are a few examples in the literature where hydrogen bonding combined with phase segregation has been investigated. Stadler and co-workers, , Lillya et al and, more recently, Duweltz et al have investigated low- T g polymers in which hydrogen-bonding groups, in the form of either 4-urazoyl benzoic acid or benzoic acid derivatives, are attached to either end of the chain. In these systems the end groups crystallize or phase segregate to form the physical cross-links which results in an enhancement of mechanical properties.…”

Section: Introductionmentioning

confidence: 99%

Utilization of a Combination of Weak Hydrogen-Bonding Interactions and Phase Segregation to Yield Highly Thermosensitive Supramolecular Polymers

et al. 2005

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Supramolecular polymerization, i.e., the self-assembly of polymer-like materials through the utilization of the noncovalent bond, is a developing area of research. In this paper, we report the synthesis and investigation of nucleobase-terminated (N6-anisoyl-adenine and N4-(4-tert-butylbenzoyl)cytosine) low molecular weight poly(THF) macromonomers (<2000 g mol(-1)). Even though the degree of interaction between the nucleobase derivatives is very low (<5 M(-1)) these macromonomers self-assemble in the solid state to yield materials with film and fiber-forming capability. While the mechanical properties of films of both materials show extreme temperature sensitivity, resulting in the formation of very low viscosity melts, they do behave differently, which is attributed to the nature of the self-assembly controlled by the nucleobase. A combination of FT-IR, WAXD, and rheological experiments was carried out to further investigate the nature of the self-assembly in these systems. The studies demonstrate that a combination of phase segregation between the hard nucleobase chain ends and the soft poly(THF) core combined with aromatic amide hydrogen bonding is utilized to yield the highly thermosensitive supramolecular polymeric materials. In addition, analysis of the data suggests that the rheological properties of these supramolecular materials is controlled by the disengagement rate of the nucleobase chain ends from the "hard" phase, which, if shown to be general, provides a design criteria in the development of more thermally responsive materials.

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“…Estimation of the molar mass of a bulk supramolecular polymer by extrapolation of values determined in solution is always questionable. Therefore, a method based on transverse relaxation measurements of bulk samples was proposed [199]. It takes advantage of the fact that the strength of residual dipolar interactions depends on the molar mass in entangled polymer melts.…”

Section: Nmr Spectroscopymentioning

confidence: 99%

Assembly via Hydrogen Bonds of Low Molar Mass Compounds into Supramolecular Polymers

Bouteiller

2007

Advances in Polymer Science

176

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Macroscopic properties of HBSPs 2.1 Rheological properties of HBSP solutions 2.1.1 Ureidopyrimidinone (UPy) 2.1.2 Benzene-tricarboxamide (BTC) 2.1.3 Cyclohexane-tricarboxamide (CTC) 2.1.4 Bis-urea 2.1.4.1 Supramolecular structure of bis-urea 3 2.1.4.2 Properties of the thin filament structure 2.1.4.3 Properties of the tubular structure 2.1.5 Oligopeptides 2.2 Material properties of bulk HBSPs 2.2.1 Amorphous glasses 2.2.2 Macroscopic fiber formation 2.2.3 Elastic materials 2.3 Liquid crystallinity 3 Engineering possibilities 3.1 Improving the strength of the association 3.2 Influence of the solvent 3.3 Tuning the ring-chain equilibrium 3.4 Copolymers 3.5 Introducing branches or crosslinks 3.6 Responsiveness induced by external triggers 3.7 Chirality 3.8 Coupling electro-optical properties 3.9 Polarity of the chain 3.10 Chain stoppers 3.11 Surface grafting 3.12 Covalent capture 4 Molar mass measurement 4.1 Size exclusion chromatography (SEC) 4.2 Light scattering 4.3 Small angle neutron scattering (SANS) 4.4 Viscosimetry 4.5 Vapor pressure osmometry (VPO) 4.6 NMR spectroscopy 4.7 FTIR spectroscopy 4.8 Fluorescence spectroscopy 4.9 Isothermal titration calorimetry (ITC)

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Supramolecular association of acid-terminated polydimethylsiloxanes. IV. NMR investigation of hydrogen bonding interactions and apparent molecular weight in the bulk state

Cited by 11 publications

References 15 publications

Supramolecular Polymerizations and Main-Chain Supramolecular Polymers

Supramolecular Polymerizations and Main-Chain Supramolecular Polymers

Utilization of a Combination of Weak Hydrogen-Bonding Interactions and Phase Segregation to Yield Highly Thermosensitive Supramolecular Polymers

Assembly via Hydrogen Bonds of Low Molar Mass Compounds into Supramolecular Polymers

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