Viscoelastic properties of linear associating poly(n-butyl acrylate) chains

Hawke, Laurence; Ahmadi, Mostafa; Goldansaz, Hadi; Ruymbeke, Evelyne Van

doi:10.1122/1.4942231

Cited by 80 publications

(158 citation statements)

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“…This comparison provides general information about the influence of associative group's strength on dynamic properties of supramolecular polymer networks in the melt state. The predicted zones for dynamic moduli‐frequency curve (in medium and low frequencies) in Hawke's model can be found for both systems . The final relaxation is hindered and the slope of Log G ′‐ Log frequency curve deviates from 2 in AA as well as UPy based systems.…”

Section: Resultsmentioning

confidence: 75%

“…M e is the entanglement molar mass of the precursor chains (16.5 kg. mol −1 ), and the M e app is the apparent entanglement molar mass of the supramolecular polymers. N s is the number of active stickers per chain, and M n is the average molar mass of the precursor polymer.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, Hawke et al have considered 4 zones in dynamic moduli‐frequency curve of supramolecular polymer networks: (1) the Rouse motion regime at high frequencies, (2) first plateau zone, (3) the constraint release Rouse relaxation of trapped segments and free dangling ends, and (4) the second plateau zone. Although they ignored pairwise associations of supramolecular moieties, their model could predict the rheological behavior of supramolecular networks based on P(BA‐ ran ‐AA) …”

Section: Introductionmentioning

confidence: 99%

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Dynamics of entangled supramolecular polymer networks in presence of high‐order associations of strong hydrogen bonding groups

Jangizehi

Ghaffarian

Ahmadi

2017

Polymers for Advanced Techs

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Dynamics of entangled polymer chains in the melt state are deliberately excluded in most of the studies on supramolecular polymer networks by utilizing nonentangled precursor chains. Relaxation of the system mainly depends on the dissociation of the associative groups in latter case and nonentangled chains deliver nothing to resist afterward. Conversely, in an entangled system, relaxation of polymer chains and dissociation of associative groups can occurred parallel.Supramolecular networks based on an entangled precursor polymer with different levels of strong associating ureidopyrimidinone (UPy) groups are synthesized to screen the corresponding effects on the dynamics of the system. Binary-associated UPy groups phase separate into collective assemblies by stacking and form high-order, needle-like domains at higher UPy contents. Relaxation of polymer chains is significantly hindered due to the trapping of polymer segments between UPy stacks. Above a certain threshold of UPy content (~4 mol%), the plateau level and final relaxation time of networks show a significant jump, which is attributed to the onset of high-order association of UPy groups. KEYWORDS chain dynamics, high-order associations, supramolecular networks 1 | INTRODUCTION Supramolecular polymer networks are macromolecular structures in which a fraction of covalent bonds are replaced with transient associations, 1-6 such as ionic attractions, 7-11 metal-ligand coordinations, [12][13][14][15][16][17] hydrogen bondings, 18-21 or π-π interactions. 22,23 Such transient bonds are in the dynamic equilibrium between associated and dissociated states. Consequently, supramolecular polymer networks response to the external stimuli and have potential to use for designing electronic, 24,25 optic-electronic, 26,27 drug-delivery, 28-32 and/or selfhealing 17,33-40 materials. The supramolecular polymer networks are divided in 2 general types. In the first type, the polymeric building blocks have associative groups at both extremities, and the virtual molar mass is increased by chain extension due to the self-assembly of end groups.In the second type, the linear or branched polymer chains carry pendant associative "sticky" groups. 41 Hydrogen bonding moieties are widely used for designing supramolecular polymers, since they demonstrate very broad range of strength, which can be controlled by the number and the configuration of the interactions. 42,43 One of these promising moieties is ureidopyrimidinone (UPy) group, which self-assembles with highstrength, quadruple hydrogen bonds. [44][45][46][47][48][49][50] Low molar mass telechelic polymers that are viscous liquid at room temperature show properties like solid polymers after functionalization with UPy groups. [51][52][53][54][55][56][57] Binary-associated UPy moieties create π-π stacking when the UPy motifs are linked to the building block chains by urethane or urea groups, which can form lateral-secondary interactions. 56,[58][59][60] The formation of micrometer long fibers in the morphology of UPy-functionalized...

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Section: Resultsmentioning

confidence: 75%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Dynamics of entangled supramolecular polymer networks in presence of high‐order associations of strong hydrogen bonding groups

Jangizehi

Ghaffarian

Ahmadi

2017

Polymers for Advanced Techs

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“…In the present case, the static branch points are the hydrogen-bonding interactions that provide the additional friction that slows down the global relaxation of the chains. 54 This additional friction/relaxation is referred to as sticky reptation and a relevant scaling theory has been proposed to account for this. 55,56 However, the unfunctionalized PNB, synthesized via ROMP of norbornene exhibits a signature η 0 power law relationship with M w , consistent with models on linear monodisperse polymers ( Figure 6).…”

Section: ■ Introductionmentioning

confidence: 99%

Catalytic Synthesis of Secondary Amine-Containing Polymers: Variable Hydrogen Bonding for Tunable Rheological Properties

Perry¹,

Ebrahimi

Morgan³

et al. 2016

Macromolecules

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A synthetic protocol using atom-economic, catalytic hydroaminoalkylation and ring-opening metathesis polymerization (ROMP) has been developed for the versatile synthesis of a new class of aryl-substituted secondary aminecontaining polymers. This catalytic route minimizes waste generation and avoids protection/deprotection protocols, postpolymerization modification, and byproduct formation. Different amines can be readily incorporated to access variable hydrogen-bonding characteristics. Thermal and melt rheological characterization has shown the profound effect of hydrogen bonding on the bulk properties of these amine-containing norbornene polymers. ■ INTRODUCTIONThere is growing interest in developing approaches to synthesize amine-containing polymers due to their diverse range of applications including antimicrobial materials, 1−5 compatibilizers for polymer blends, 6−8 CO 2 uptake, 9−11 water purification, 12,13 and catalytic materials. 14−20 Current strategies for the synthesis of these high-value products are often plagued by multistep monomer syntheses with inefficient protection/ deprotection protocols 1,21−23 and/or the use of postpolymerization modifications. 24,25 These traditional routes often result in limited control over amine functionalization and poorly defined polymer microstructures. 26 In recent years, ROMP 20 has emerged as a powerful tool for the synthesis of functionalized polymers including polyamides. 27−30 Notably, ROMP conditions rarely tolerate free primary or secondary pendant amine groups, 31,32 presumably due to the fact that these nucleophilic and sterically accessible amines can coordinate and decompose catalytic Ru species. 33 More recently, select norbornene monomers with tertiary or secondary alkylamines have been shown to undergo ROMP using a newly reported cationic Mo alkylidene metathesis catalyst. 34 However, these reports involve multistep synthetic protocols and stoichiometric reagents to access the requisite norbornene substrates. Thus, to date, the controlled polymerization of unprotected amine-containing monomers has not been a practical and efficient strategy for accessing this broadly useful class of materials.Our approach for addressing synthetic challenges in aminecontaining polymer synthesis exploits our recently developed hydroaminoalkylation catalysts, 35,36 coupled with promising results in ROMP of functionalized monomers (Scheme 1). 37 Hydroaminoalkylation is an α-C−H alkylation reaction of secondary amines with alkene substrates. 36 By using our N,Ochelated tantalum phosphoramidate precatalyst 1, 35 amine functionalized, cyclic alkene monomers can be prepared in one solvent-free, atom-economic reaction of cyclic diene precursors (Scheme 2). Thus, these two catalytic strategies can be combined to access a flexible and modular synthetic approach while realizing optimized atom and step efficiency. Importantly, hydroaminoalkylation yields unprotected secondary amines that participate in hydrogen bonding to give amine-containing polymers with tunable physical and me...

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“…In the present context, ionomers also structurally resemble the phase separation [28][29][30]. Likewise, metallo-intermediated supramolecular associations which tend to form homogeneous systems are known to behave in a similar way as well [31][32][33]. Their use is, however, limited related to the mixing of the components.…”

Section: Introductionmentioning

confidence: 98%

Supramolecular Dimerization in a Polymer Melt from Small-Angle X-ray Scattering and Rheology: A Miscible Model System

et al. 2020

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We present a structural and dynamic study on the simplest supramolecular hetero-association, recently investigated by the authors to prepare architectural homogeneous structures in the melt state, based on the bio-inspired hydrogen-bonding of thymine/diaminotriazine (thy–DAT) base-pairs. In the combination with an amorphous low Tg poly(butylene oxide) (PBO), no micellar structures are formed, which is expected for nonpolar polymers because of noncompatibility with the highly polar supramolecular groups. Instead, a clear polymer-like transient architecture is retrieved. This makes the heterocomplementary thy–DAT association an ideal candidate for further exploitation of the hydrogen-bonding ability in the bulk for self-healing purposes, damage management in rubbers or even the development of easily processable branched polymers with built-in plasticizer. In the present work, we investigate the temperature range from Tg + 20 °C to Tg + 150 °C of an oligomeric PBO using small-angle X-ray scattering (SAXS) and linear rheology on the pure thy and pure DAT monofunctionals and on an equimolar mixture of thy/DAT oligomers. The linear rheology performed at low temperature is found to correspond to fully closed-state dimeric configurations. At intermediate temperatures, SAXS probes the equilibrium between open and closed states of the thy–DAT mixtures. The temperature-dependent association constant in the full range between open and closed H-bonds and an enhancement of the monomeric friction coefficient due to the groups is obtained. The thy–DAT association in the melt is more stable than the DAT–DAT, whereas the thy–thy association seems to involve additional long-lived interactions.

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Viscoelastic properties of linear associating poly(n-butyl acrylate) chains

Cited by 80 publications

References 35 publications

Dynamics of entangled supramolecular polymer networks in presence of high‐order associations of strong hydrogen bonding groups

Dynamics of entangled supramolecular polymer networks in presence of high‐order associations of strong hydrogen bonding groups

Catalytic Synthesis of Secondary Amine-Containing Polymers: Variable Hydrogen Bonding for Tunable Rheological Properties

Supramolecular Dimerization in a Polymer Melt from Small-Angle X-ray Scattering and Rheology: A Miscible Model System

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