Threading of Ring Poly(ethylene oxide) Molecules by Linear Chains in the Melt

Tsalikis, Dimitrios G.; Mavrantzas, Vlasis G.

doi:10.1021/mz5002096

Cited by 67 publications

(109 citation statements)

References 8 publications

(13 reference statements)

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“…Therefore, these threading effects that connect ring and linear chains constitute long lived entanglements which represent strong topological interactions that are capable of slowing down relaxation and chain mobility. 1,[34][35][36][37][38][39][40][41] In view of the above explained arguments, a threading effect of C-PCL by L-PCL chains reduces the spherulitic growth rates of ring PCL molecules, as shown in Fig. 6.…”

Section: Spherulitic Growth Rates Determined By Plommentioning

confidence: 86%

“…6 Similar effects have been predicted by computer simulations. 1,[34][35][36][37][38][39][40][41] These studies have shown that cyclic molecules relax and diffuse more slowly than linear chains. Therefore, these threading effects that connect ring and linear chains constitute long lived entanglements which represent strong topological interactions that are capable of slowing down relaxation and chain mobility.…”

Section: Spherulitic Growth Rates Determined By Plommentioning

confidence: 99%

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The influence of small amounts of linear polycaprolactone chains on the crystallization of cyclic analogue molecules

et al. 2016

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Cyclic poly(3-caprolactone) model chains (C-PCL) were synthesized by a ring closure click chemistry technique. Identical linear precursors (L-PCL) of equivalent molecular lengths were also prepared. The effect of adding small amounts of linear (L-PCL) to cyclic analogs (C-PCL) was studied by preparing blends (C/L) in solution of the following composition range: 95/5, 90/10 and 80/20. Two sets of blends with PCL samples of different number average molecular weights (3 and 12 kg mol À1 ) were studied. The blends were analyzed by polarized light optical microscopy (PLOM) and advanced Differential Scanning Calorimetry (DSC) techniques that included non-isothermal and isothermal crystallization studies and thermal fractionation by SSA (Successive Self-nucleation and Annealing). The results show that addition of small amounts of linear chains (i.e., 5 and 10 wt%) to cyclic PCLs produces synergistic decreases in crystallization and melting temperatures, crystallinity degrees and isothermal crystallization rates (for both 3 and 12 kg mol À1 samples). When the amount of linear chains reaches 20 wt%, a significant recovery of a simple mixing law behavior is obtained. Thermal fractionation demonstrated that the addition of linear chains can reduce the annealing capacity of cyclic chains. The behavior of the C/L blends can be explained by the threading of ring molecules by linear chains. This threading effect amounts to an increase in entanglement density that reduces chain diffusion and hence crystallization rate.

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Section: Spherulitic Growth Rates Determined By Plommentioning

confidence: 86%

Section: Spherulitic Growth Rates Determined By Plommentioning

confidence: 99%

The influence of small amounts of linear polycaprolactone chains on the crystallization of cyclic analogue molecules

et al. 2016

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“…On the other hand, numerical and experimental findings (5,6) suggest that rings exhibit strong intercoil correlations, which have proved difficult to address in simplified theoretical models (9)(10)(11)(12). Because of this, there have been many recent attempts to rigorously characterize these interchains' interactions (13)(14)(15)(16), although a precise definition and unambiguous identification of these "threadings" in concentrated solutions of rings remains elusive. The primary reason for this is that the rings are assumed to remain strictly topologically unlinked from one another throughout if synthesized in this state.…”

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confidence: 99%

A topologically driven glass in ring polymers

Michieletto

Turner

2016

Proc. Natl. Acad. Sci. U.S.A.

112

185

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The static and dynamic properties of ring polymers in concentrated solutions remains one of the last deep unsolved questions in polymer physics. At the same time, the nature of the glass transition in polymeric systems is also not well understood. In this work, we study a novel glass transition in systems made of circular polymers by exploiting the topological constraints that are conjectured to populate concentrated solutions of rings. We show that such rings strongly interpenetrate through one another, generating an extensive network of topological interactions that dramatically affects their dynamics. We show that a kinetically arrested state can be induced by randomly pinning a small fraction of the rings. This occurs well above the classical glass transition temperature at which microscopic mobility is lost. Our work both demonstrates the existence of long-lived inter-ring penetrations and realizes a novel, topologically induced, glass transition.glass transition | ring polymers | topology | topological glass | molecular dynamics T he physics of ring polymers remains one of the last big mysteries in polymer physics (1). Concentrated systems of ring polymers have been observed, in both simulations and experiments, to display unique features that are not easily reconciled with the standard reptation theory of linear polymers (2-6). The main reason for this is that ring polymers do not possess free terminal segments, or ends, essential for end-directed curvilinear diffusion. In contrast, ring polymers possess a closed contour, which leads to markedly different relaxation and diffusion mechanisms. Recently, there has been much improvement in the production of purified systems of rings (6-8), with the consequent result that more and more experimental puzzling evidence requires a deeper understanding of their motion in concentrated solutions and melts from a theoretical point of view.Recently, it has been conjectured that ring polymers assume crumpled, segregated conformations in concentrated solution or the melt (5). On the other hand, numerical and experimental findings (5, 6) suggest that rings exhibit strong intercoil correlations, which have proved difficult to address in simplified theoretical models (9-12). Because of this, there have been many recent attempts to rigorously characterize these interchains' interactions (13-16), although a precise definition and unambiguous identification of these "threadings" in concentrated solutions of rings remains elusive. The primary reason for this is that the rings are assumed to remain strictly topologically unlinked from one another throughout if synthesized in this state.In the case of concentrated solutions of rings embedded in a gel, a method to identify these interpenetrating threadings has recently been proposed (13). Here it was shown that the number of threadings scales extensively in the polymer length (or mass) and can therefore be numerous for long rings, creating a hierarchical sequence of constraints that can span the entire system. It has also been con...

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“…Phenomena in which topological effects play a role include the Quantum Hall effect [1], superconductivity [2], topological insulators [3], spin liquids [4], and defect behavior in crystals [5]. Due to the variety of and control over their connectivity, polymers are particularly interesting for exploring topological effects on physical properties, including polymer rheology [6][7][8][9] and thermodynamics [10][11][12][13][14][15][16][17][18]. In particular, polymer melts containing cyclic or long-branched chains have rheology and chain dynamics [13] that can differ dramatically with architecture and are different from those of linear analogs.…”

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confidence: 99%

Evidence and Limits of Universal Topological Surface Segregation of Cyclic Polymers

Wang

et al. 2017

Phys. Rev. Lett.

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Threading of Ring Poly(ethylene oxide) Molecules by Linear Chains in the Melt

Cited by 67 publications

References 8 publications

The influence of small amounts of linear polycaprolactone chains on the crystallization of cyclic analogue molecules

The influence of small amounts of linear polycaprolactone chains on the crystallization of cyclic analogue molecules

A topologically driven glass in ring polymers

Evidence and Limits of Universal Topological Surface Segregation of Cyclic Polymers

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