High Molecular Weight Supramolecular Polymers Containing Both Terpyridine Metal Complexes and Ureidopyrimidinone Quadruple Hydrogen-Bonding Units in the Main Chain

Hofmeier, H Harald; Hoogenboom, Richard; Wouters, Mel Marielle; Schubert, Ulrich S.

doi:10.1021/ja042919e

Cited by 229 publications

(119 citation statements)

References 37 publications

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“…Supramolecular polymers are made of covalent chains connected through reversible interactions, such as hydrogen bonding , metal-ligand coordination [26][27][28][29][30][31][32][33][34][35][36][37][38], and ionic aggregation [39][40][41][42][43][44][45]. The ability to vary and control the interactions in supramolecular systems provides an efficient tool to tune the structure, dynamics and rheology [26,29,46].…”

Section: Introductionmentioning

confidence: 99%

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

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Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate based polymers for which the concentration of randomly distributed supramolecular side-groups are systematically varied. We perform a detailed investigation of the appplicability of Time Temperature Superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the "stickyRouse" model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the "sticky-Rouse" model, which includes more realistic assumptions with regards to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends and (iii) the chain motion upon dissociation of a sticker and re-association with a new co-ordination which involves a finite sized "hop" of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology. * k.j.l.mattsson@leeds.ac.uk 2

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Section: Introductionmentioning

confidence: 99%

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

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“…Strategies to control the size and shape of nano-and micrometer size objects that rely on selective solvent techniques in the self-assembly of block copolymers will not be discussed here. [60][61][62][63][64][65][66][67][68][69][70][71][72][73] Supramolecular multicomponent gels, [74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89] or orthogonal self-assembly, [90][91][92][93][94][95][96][97] self-sorting [98][99][100][101][102][103][104] and chiral amplification strategies 105 in multicomponent supramolecular polymers will not be covered in detail, and the interested reader is referred to the recent literature and review articles.…”

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confidence: 99%

Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

128

102

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The self-assembly into supramolecular polymers is a process driven by reversible non-covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli-responsive properties: (1) endcapping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of selfassembly kinetics of synthetic supramolecular systems. V C 2016

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“…Among them, ureidopyrimidone (UPy) derivatives [24,26,[33][34][35] present four hydrogen bonds with strong associations. UPy can be in equilibrium between its two tautomers, AADD or ADAD patterns, [36] both of which are self-associated in homodimers.…”

Section: Introductionmentioning

confidence: 99%

Polystyrene supramolecular networks based on DA-AD hydrogen bonds

Becquart

Adidou

et al. 2015

Designed Monomers and Polymers

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Then polystyrene supramolecular networks were prepared by radical copolymerization of styrene with monomers containing donor-acceptor (DA) moieties methacrylamide (MAAM) or 2-methacrylamidopyridine (MAP). The molar percentages of MAAM and MAP in the copolymers were, respectively, 2-20% and 6-40%. The glass transition temperatures (T g s) of these copolymers have been modeled by the Kwei equation showing secondary interactions due to intermolecular hydrogen bonds. The DA-AD association constants (K) have been calculated by 1 H NMR spectroscopy of MAAM and MAP. These constants were, respectively, 6.75 and 16.75 M −1 . Dynamic mechanical analyses by frequency and temperature sweep tests, were carried out in the molten state. Styrene-MAP or styrene-MAAM copolymers had higher moduli than neat polystyrene but the MAP influences the materials' properties distinctively from the MAAM. MAP copolymers had a second G′ plateau that appeared at 150°C, thus showing the formation of a supramolecular network.

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High Molecular Weight Supramolecular Polymers Containing Both Terpyridine Metal Complexes and Ureidopyrimidinone Quadruple Hydrogen-Bonding Units in the Main Chain

Cited by 229 publications

References 37 publications

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Controlling supramolecular polymerization through multicomponent self‐assembly

Polystyrene supramolecular networks based on DA-AD hydrogen bonds

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